Surface-treated aggregated boron nitride powder, aggregated boron nitride powder, and thermally conductive resin composition

ABSTRACT

A surface-treated aggregated boron nitride powder is prepared by using the boron nitride powder as the raw material, adding an oxidizer to the boron nitride aggregated grains, wet-pulverizing or wet-crushing the grains for surface modification treatment of the particles and allowing reaction of the particles with a metal coupling agent. The surface-treated boron nitride aggregated grains are formed by aggregation of hexagonal h-BN primary particles; (B) have any one or more of Si, Ti, Zr, Ce, Al, Mg, Ge, Ga, and V in an amount of 0.1 atm % or more and 3.0 atm % or less in its composition on the surface of 10 nm; (C) have a crushing strength of 5 MPa or more; and (D) have an average particle diameter of 20 μm or more and 100 μm or less.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional patent application of Ser. No. 16/339,978 filed onApr. 5, 2019, which is National Phase of International Application No.PCT/JP2017/031355 filed Aug. 31, 2017, and claims priorities fromJapanese Applications No. 2016-198961, filed Oct. 7, 2016 and No.2016-229343 filed Nov. 25, 2016, the disclosures of which are herebyincorporated by reference herein in its entirety.

TECHNICAL FIELD

The present invention relates to a surface-treated aggregated boronnitride (BN) powder, aggregated boron nitride powder, and thermallyconductive resin composition.

BACKGROUND ART

It is an important problem for heat-generating electronic parts such aspower devices, transistors, thyristors, and CPUs to dissipateefficiently the heat generated during use. Generally as measures forsuch heat dissipation, (1) the thermal conductance of the insulationlayer formed on the printed wiring board on which heat-generatingelectronic parts are mounted was increased or (2) a heat-generatingelectronic part or a printed wiring board carrying a heat-generatingelectronic part was adhered to a heat sink via an electricallyinsulating thermal interface material. A mixture of a silicone or epoxyresin with a ceramic powder has been used for the insulation layer ofprinted wiring boards and the thermal interface material.

Recently, increase in speed and integration of circuits inheat-generating electronic parts and also increase in mounting densityof heat-generating electronic parts on printed wiring boards lead toincreased heat generation density in electronic devices, year by year.There is thus an increasing demand for a higher-thermal conductivityceramic powder.

Under the circumstances above, a hexagonal boron nitride powder, whichhas favorable properties as an electrical insulating material such ashigh thermal conductivity, high insulating property, and low dielectricconstant, is attracting attention.

However, the hexagonal boron nitride particles, which have a thermalconductivity of 400 W/(m·K) in the in-plane direction (a-axisdirection), but have a thermal conductivity of 2 W/(m·K) in thethickness direction (c-axis direction), show large anisotropy in thermalconductivity due to their crystal structure and scaly shape. Furtherwhen the hexagonal boron nitride powder is mixed with a resin, theparticles are oriented in the same direction.

As a result, the in-plane direction (a-axis direction) of the hexagonalboron nitride particle becomes vertical to the thickness direction ofthe thermal interface material, for example during production of athermal interface material, prohibiting efficient utilization of thehigh thermal conductivity of the hexagonal boron nitride particle in thein-plane direction (a-axis direction).

Patent Document 1 proposes a product in which the in-plane direction(a-axis direction) of hexagonal boron nitride particles are oriented inthe thickness direction of a high-heat conduction sheet, and such aproduct utilizes efficiently the high thermal conductivity of thehexagonal boron nitride particle in the in-plane direction (a-axisdirection).

However, it is needed to (1) laminate the oriented sheet in thefollowing step, making the production process complicated, and to (2)cut the product to a thin sheet after lamination and hardening, makingit difficult to ensure the dimensional accuracy of the thickness of thesheet. As the hexagonal boron nitride particles have a scaly shape, theylead to increase in viscosity and decrease in flowability when mixedwith a resin, prohibiting mixing at a higher rate.

Boron nitride powders in various shapes that are smaller in theanisotropy in thermal conductivity of the hexagonal boron nitrideparticles were proposed to overcome these problems.

Patent Document 2 proposes a boron nitride powder smaller in anisotropyin thermal conductivity in which the primary-particle hexagonal boronnitride particles are aggregated as they are not oriented in the samedirectional.

Aggregated boron nitrides prepared by other known production methodsinclude a spherical boron nitride prepared by spray-drying method(Patent Document 3), an aggregated boron nitride prepared using boroncarbide as the raw material (Patent Document 4), and an aggregated boronnitride prepared by repeated pressurization and crushing (PatentDocument 5).

CITATION LIST Patent Documents

Patent Document 1: JP-A No. 2000-154265

Patent Document 2: JP-A No. H09-202663

Patent Document 3: JP-A No. 2014-40341

Patent Document 4: JP-A No. 2011-98882

Patent Document 5: JP-T No. 2007-502770

Patent Document 6: JP-A No. 2011-98882

Patent Document 7: JP-T No. 2007-502770

Patent Document 8: JP-A No. 2006-257392

Patent Document 9: JP-A No. 2015-36361

SUMMARY OF THE INVENTION Technical Problem

However, the aggregate particles prepared by the method described inPatent Document 1 had lower grain strength and disintegrated even underweak shearing stress, and thus did not give sufficiently high heatconductivity.

The aggregated boron nitride powder described in Patent Document 2, thespherical boron nitride described in Patent Document 3, the aggregatedboron nitride described in Patent Document 4, and the aggregated boronnitride described in Patent Document 5 had a crushing strength of 5.1MPa or less and were not strong enough for processing in high-stressmeans such as three-roll mills, ultrasonicators and presses in theprocess of mixing with a resin and sheeting of the mixture from theviewpoint of aggregation strength. There is thus a demand for ahigher-strength aggregated boron nitride powder.

A main object of the present invention is to provide a boron nitridepowder superior in thermal conductivity and higher in grain strength.

Solution to Problem

After intensive studies, the inventors have made the present invention.

Specifically, the inventors have made intensive studies on a boronnitride powder containing boron nitride aggregated grains prepared fromboron carbide as the raw material. As a result, the inventors have foundthat it is possible to produce a boron nitride powder containing boronnitride aggregated grains that are higher in grain strength and uniformin primary particle size, have a dense structure and are thus favorableas a thermally conductive filler, by (a) pressure-nitridating andcalcining a boron carbide adjusted to a particular average particlediameter and a carbon content in a pressure-nitridating and calciningstep and (b) heating the boron carbide nitride after pressurenitridation and calcination to a temperature allowing initiation ofdecarburization, heating it to a retention temperature at a particularheating rate and heating it at the particular temperature for a certainperiod in a decarburization crystallization step.

Patent Document 4 describes a method for producing a hexagonal boronnitride powder, wherein the hexagonal boron nitride powder is subjectedto a reduced pressure treatment under a furnace internal pressure heldat less than 100 KPa after the decarburization treatment (e.g., seeClaim 6 and FIG. 1).

Alternatively, Patent Document 5 describes a method for producing anaggregated boron nitride powder, wherein a raw material boron nitridehaving an average crystal size of 5 μm or less (favorably, 2 μm or less)is once heat-treated and the resulting aggregate is pulverized andclassified repeatedly (e.g., see original Claims 30 to 33, Examples 1 to7, and FIG. 1).

Thus, the production method according to the present invention isdifferent in its characteristic configuration and technological ideafrom these production methods.

The inventors have found that the aggregated boron nitride powderdescribed above is a boron nitride powder (A) containing aggregates ofscaly hexagonal boron nitride primary particles having a size in aparticular range, (B) containing boron nitride aggregated grains havinga high grain strength and (C) having a particular average particlediameter and also that the boron nitride powder is a new compound. Theinventors also found that it is possible to produce an aggregated boronnitride powder further superior in filling property into resin to thisnew boron nitride powder by subjecting the new compound to a specialsurface treatment. Accordingly, the present invention provides thefollowing inventions [1] to [11].

The present invention provides the followings:

[1] A boron nitride powder comprising boron nitride aggregated grainsthat are formed by aggregation of scaly hexagonal boron nitride primaryparticles, the boron nitride powder having the following characteristics(A) to (C):(A) the primary particles of the scaly hexagonal boron nitride have anaverage long side length of 1.5 μm or more and 3.5 μm or less and astandard deviation of 1.2 μm or less;(B) the boron nitride aggregated grains have a grain strength of 8.0 MPaor more at a cumulative breakdown rate of 63.2% and a grain strength of4.5 MPa or more at a cumulative breakdown rate of 20.0%; and(C) the boron nitride powder has an average particle diameter of 20 μmor more and 100 μm or less.[2] The boron nitride powder described in [1] above, wherein the averageparticle diameter of the boron nitride powder (C) is 30 μm or more and80 μm or less.[3] The boron nitride powder described in [1] or [2] above, prepared bya method for producing a boron nitride powder characterized by the stepsof;(a) pressure-nitridating and calcining a boron carbide having an averageparticle diameter of 6 μm or more and 55 μm or less and a carbon contentof 18% or more and 21% or less and(b) heat-treating the boron carbide by heating it to a temperatureallowing initiation of decarburization, heating it to a retentiontemperature at a heating rate of 5° C./min or less, and heating it at atemperature of 1750° C. or higher for a period longer than 0.5 hour andshorter than 40 hours in a decarburization crystallization step afterthe pressure nitridation and calcination.[4] The boron nitride powder described in [3] above, wherein the boroncarbide is pressure-nitridated and calcined at a temperature of 1800° C.or higher and at a pressure of 0.7 MPa or more and 1.0 MPa or less inthe step (a).

The present invention also provides the followings:

[5] A surface-treated aggregated boron nitride powder, prepared by usingthe boron nitride powder described in [1] or [3] above as the rawmaterial, adding an oxidizer to the boron nitride aggregated grains,wet-pulverizing or wet-crushing the grains for surface modificationtreatment of the particles, and allowing reaction of the particles witha metal coupling agent, the powder having the following characteristics(A) to (D):(A) the surface-treated boron nitride aggregated grains are formed byaggregation of hexagonal h-BN primary particles;(B) the surface-treated boron nitride aggregated grains have any one ormore of Si, Ti, Zr, Ce, Al, Mg, Ge, Ga, and V in an amount of 0.1 atm %or more and 3.0 atm % or less in its composition on the surface of 10nm;(C) the surface-treated boron nitride aggregated grains have a crushingstrength of 5 MPa or more; and(D) the surface-treated aggregated boron nitride powder has an averageparticle diameter of 20 μm or more and 100 μm or less.[6] The surface-treated aggregated boron nitride powder described in [5]above, prepared as the oxidizer and a water-soluble solvent are addedduring the surface modification treatment.[7] The surface-treated aggregated boron nitride powder described in [5]or [6] above, wherein the metal coupling agent is one or more couplingagents selected from titanium coupling agents, silane coupling agents,zirconium coupling agents, and aluminum coupling agents.

The present invention further provides the followings:

[8] An aggregated boron nitride powder, characterized by having thefollowing characteristics (A) to (D):(A) the boron nitride aggregated grains are formed by aggregation ofhexagonal h-BN primary particles;(B) the boron nitride aggregated grains have any one or more of Si, Ti,Zr, Ce, Al, Mg, Ge, Ga, and V in an amount of 0.1 atm % or more and 3.0atm % or less in its composition on the surface of 10 nm;(C) the boron nitride aggregated grains have a crushing strength of 5MPa or more; and(D) the aggregated boron nitride powder has an average particle diameterof 20 μm or more and 100 μm or less.[9] The aggregated boron nitride powder described in [8] above,characterized additionally by having the following characteristic:(E) the boron nitride aggregated grains have organic functional groupson the surface.[10] The aggregated boron nitride powder described in [8] or [9] above,wherein the organic functional group present on the surface of the boronnitride aggregated grains is one or more groups selected from epoxygroups that may be substituted, styryl groups that may be substituted,alkyl groups that may be substituted, vinyl groups that may besubstituted, acetylacetate groups that may be substituted, acyl groupsthat may be substituted, isocyanate groups that may be substituted,cyclohexyl groups that may be substituted, and tetraoctyl bis(ditridecylphosphite) groups that may be substituted.

The present invention further provides the following:

[11] A thermally conductive resin composition, comprising the aggregatedboron nitride powder described in [1], [5] or [8] above.

Advantageous Effects of Invention

The present invention provides a boron nitride powder superior inthermal conductivity and higher in grain strength. It should beunderstood that the advantageous effects described herein are notparticularly limited and may be any of the effects described in thepresent description.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a photograph of the boron nitride powder prepared by theproduction method in the first embodiment of the present invention. Theboron nitride powder contains boron nitride aggregated grains.

FIG. 2 is a scanning electron micrograph of the boron nitride aggregatedgrains present in the boron nitride powder prepared by the productionmethod in the first embodiment of the present invention. FIG. 2 showsthe boron nitride aggregated grains.

FIG. 3 is a scanning electron micrograph showing a sectional view of theboron nitride aggregated grains present in the boron nitride powderprepared by the production method in the first embodiment of the presentinvention. It is shown that multiple scaly hexagonal boron nitride(primary particles) are present in the boron nitride aggregated grains.The photograph also shows that multiple primary particles make a bulkymass by aggregation, forming a boron nitride aggregated grain.

DESCRIPTION OF EMBODIMENTS

Hereinafter, favorable embodiments of the present invention will bedescribed. The embodiments described below are only examples of thetypical embodiments of the present invention and it should be understoodthat the scope of the present invention shall not be restricted thereby.

The first and second embodiments of the present invention relate toboron nitride aggregated grains, a method for producing the same, and athermally conductive resin composition comprising the same.

More specifically, the first and second embodiments of the presentinvention relates to a boron nitride (BN) powder, a method for producingthe same and an application thereof. In particular, the first and secondembodiments of the present invention relates to a boron nitride powder,a method for producing the same and a thermally conductive resincomposition comprising the same.

<1-1. Boron Nitride Powder in the First Embodiment of the PresentInvention>

The first embodiment according to the present invention relates to aboron nitride powder comprising boron nitride aggregated grains that areformed by aggregation of the following scaly hexagonal boron nitrideprimary particles (A) (e.g., see FIGS. 1 to 3).

The boron nitride powder preferably has a carbon content of 0.2% orless, more preferably 0.1% or less.

(A) The primary particles of the scaly hexagonal boron nitridepreferably have an average long side length of 1.5 μm or more and 3.5 μmor less and a standard deviation of 1.2 μm or less.(B) The aggregated grains of the aggregated boron nitride powderpreferably have a grain strength of 8.0 MPa or more at a cumulativebreakdown rate of 63.2% and a grain strength of 4.5 MPa or more at acumulative breakdown rate of 20.0%.(C) The boron nitride powder preferably has an average particle diameterof 20 μm or more and 100 μm or less.

<1-1. (A) Scaly Hexagonal Boron Nitride (Primary Particles)>

The primary particles of “(A) the scaly hexagonal boron nitride (primaryparticles)” in the first embodiment of the present invention preferablyhave an average long side length of 1.5 μm or more and 3.5 μm or less,more preferably 1.7 μm or more and 3.2 μm or less, yet more preferably2.0 μm or more and 3.0 μm or less.

When the primary particles have an average long side length of more than3.5 μm, aggregated grains formed by aggregation of the primary particlesmay become coarser inside, leading to deterioration in grain strength.Alternatively when the primary particles have an average long sidelength of less than 1.5 μm, the primary particles may become smaller,leading to deterioration in thermal conductivity.

The primary particles of the “(A) scaly hexagonal boron nitride (primaryparticles)” in the first embodiment of the present invention preferablyhave a standard deviation of long side length at 1.2 μm or less, morepreferably 1.0 μm or less, and yet more preferably 0.8 μm or less. Whenthe standard deviation is more than 1.2 μm, the particles may not have auniform structure, leading to deterioration in grain strength. Althoughthe minimum allowable value of the standard deviation of long sidelength of the primary particles is not particularly limited, as theparticles become more resistant to penetration by resins, possiblyleading to generation of voids and others and thus to deterioration indielectric breakdown properties when the particles have an excessivelyuniform and dense structure, the standard deviation of long side lengthof the primary particles is preferably 0.2 μm or more, more preferably0.4 μm or more.

<1-1. (B) Boron Nitride Aggregated Grains>

The aggregated grains of the “(B) boron nitride aggregated grains” inthe first embodiment of the present invention preferably have a grainstrength of 8.0 MPa or more at a cumulative breakdown rate of 63.2% anda grain strength of 4.5 MPa or more at a cumulative breakdown rate of20.0%. When the aggregated grains have a grain strength smaller thanthat described above, the aggregate particles may be broken down by thestress caused by kneading with resin or pressurization, possibly leadingto deterioration in thermal conductivity.

The aggregated grains more preferably have a grain strength of 8.0 MPaor more, yet more preferably 9.0 MPa or more, at a cumulative breakdownrate of 63.2%.

The maximum allowable value of the grain strength of the aggregatedgrains at a cumulative breakdown rate of 63.2% is not particularlylimited, but may be, for example, 50 MPa, 40 MPa, 30 MPa, or 20 MPa.

The aggregated grains more preferably have a grain strength of 4.5 MPaor more, yet more preferably 5.0 MPa or more, at a cumulative breakdownrate of 20.0%. The maximum allowable value of the grain strength of theaggregated grains at a cumulative breakdown rate of 20.0% is notparticularly limited, but may be, for example, 20 MPa or 13 MPa.

High-strength boron nitride aggregated grains are preferable for use asa raw material during the surface modification treatment in the <2-1.aggregated boron nitride fine powder in the third embodiment of thepresent invention> described below, and higher-strength boron nitrideaggregated grains, such as the aggregated grains having a grain strengthof 20 MPa to 50 MPa at a cumulative breakdown rate of 63.2%, are morepreferable.

<1-1. (C) Boron Nitride Powder>

The boron nitride powder of the “(C) boron nitride powder” in the firstembodiment of the present invention preferably has an average particlediameter of 20 μm or more, more preferably 22 μm or more, yet morepreferably 30 μm or more.

The boron nitride powder preferably has an average particle diameter of100 μm or less, more preferably 90 μm or less, yet more preferably 80 μmor less.

The boron nitride powder preferably has an average particle diameter of20 μm or more and 100 μm or less, more preferably 30 μm or more and 80μm or less.

An average particle diameter of less than 20 μm may lead todeterioration in thermal conductivity, as the average particle diameterbecomes too small. Alternatively, an average particle diameter of morethan 100 μm may make it difficult to prepare a sheet, as the differencein thickness between the average particle diameter of the boron nitridepowder and the heat dissipation sheet becomes smaller.

The boron nitride powder in the first embodiment of the presentinvention preferably has a thermal conductivity of 10 W/mK or more.

The first embodiment according to the present invention provides a boronnitride powder superior in thermal conductivity and aggregated grainstrength.

The boron nitride powder in the first embodiment of the presentinvention is used favorably as a raw material for heat-dissipating partsin heat-generating electronic parts, such as power devices, inparticular as a material to be blended into resin compositions for aninsulation layer or a thermal interface material of printed wiringboards.

<1-2. Method for Producing a Boron Nitride Powder in the FirstEmbodiment of the Present Invention>

The boron nitride powder in the first embodiment of the presentinvention can be prepared by (a) pressure-nitridating and calciningboron carbide and (b) decarburizing and crystallizing the baked productafter calcining.

The method for producing a boron nitride powder according to the presentinvention comprises the following steps (a) and (b) of

(a) pressure-nitridating and calcining a boron carbide having an averageparticle diameter of 6 μm or more and 55 μm or less and a carbon contentof 18% or more and 21% or less, and(b) heat-treating the boron carbide by heating it to a temperatureallowing initiation of decarburization, heating it to a retentiontemperature at a heating rate of 5° C./min or less, and heating it at atemperature of 1750° C. or higher for a period longer than 0.5 hour andshorter than 40 hours in a decarburization crystallization step afterthe pressure nitridation and calcination.

<1-2. (a) Pressure-Nitridating and Calcining Step>

In the “(a) pressure-nitridating step” of the method for producing aboron nitride powder in the first embodiment of the present invention,the boron carbide having an average particle diameter of 6 μm or moreand 55 μm or less and a carbon content of 18% or more and 21% or less ispressure-nitridated and calcined under an atmosphere at a particularcalcining temperature and application pressure, giving a boron carbidenitride.

<1-2. (a1) Raw Material Boron Carbide Used in Pressure-Nitridating Step>

As the particle diameter of the raw material boron carbide used in thepressure-nitridating step has a significant influence of the grain sizeof the boron nitride aggregated grains finally prepared, a boron carbidehaving a proper particle diameter should be selected and use of a rawmaterial boron carbide having an average particle diameter of 7 μm ormore and 45 μm or less is desirable. It is desirable that the rawmaterial contains a smaller amount of impurities such as boric acid andisolated carbon.

The minimum allowable value of the average particle diameter of theboron carbide is preferably 6 μm or more, more preferably 7 μm or more,yet more preferably 10 μm or more.

The maximum allowable value of the average particle diameter of theboron carbide is preferably 55 μm or less, more preferably, 50 μm orless, yet more preferably 45 μm or less.

The average particle diameter of the boron carbide is preferably 7 to 50μm, more preferably 7 to 45 μm.

The carbon content of the raw material boron carbide used in thepressure-nitridating step is preferably lower than the content ofcomposition B₄C (21.7%) and boron carbide having a carbon content of18.0% or more and 20.5% or less is used desirably.

The minimum allowable value of the carbon content of the boron carbideis preferably 18% or more, more preferably 19% or more.

The maximum allowable value of the carbon content of the boron carbideis preferably 21% or less, more preferably 20.5% or less.

The carbon content of the boron carbide is preferably 18.0% to 20.5%. Itis because dense boron nitride aggregated grains are formed and thecarbon content in the boron nitride finally prepared becomes smallerwhen the amount of carbon vaporized in the decarburization step issmaller. It is difficult to prepare a stable boron carbide having acarbon content of less than 18%, as such a boron carbide has acomposition that deviates excessively from the theoretical composition.

Any known production method may be used as the method for producing aboron carbide and it is possible to prepare a boron carbide having adesired average particle diameter and carbon content.

For example, it is possible to prepare boron carbide lumps by mixingboric acid and acetylene black and calcining the mixture in anatmosphere of 1800 to 2400° C. for 1 to 10 hours. The lumps are thensubjected to pulverization, sieving, washing, impurity removal, drying,and others, to give a boron carbide powder.

Boric acid and acetylene black, raw materials for boron carbide, arepreferably mixed at a rate of 100 parts by mass of boric acid to 25 to40 parts by mass of acetylene black.

The atmosphere under which the boron carbide is prepared is preferablyan inert gas, and examples of the inert gases used include argon gas andnitrogen gas. These gases may be used alone or in combination, asneeded. In particular, use of argon gas is preferable.

Any common pulverizer or crusher may be used for pulverization of theboron carbide lumps and the lumps are pulverized, for example, forapproximately 0.5 to 3 hours. The boron carbide after pulverization waspreferably sieved through a sieve net into grains having a grain size of75 μm or less.

<1-2. (a2) Pressure-Nitridating and Calcining Step>

The minimum allowable value of the calcining temperature in thepressure-nitridating step is preferably 1700° C. or higher, morepreferably 1800° C. or higher. The maximum allowable value of thecalcining temperature is preferably 2400° C. or lower, more preferably2200° C. The calcining temperature is more preferably 1800 to 2200° C.

The minimum allowable value of the pressure in the pressure-nitridatingstep is preferably 0.6 MPa or more, more preferably 0.7 MPa or more. Themaximum allowable value of the calcining temperature is preferably 1.0MPa, more preferably 0.9 MPa. The pressure is more preferably 0.7 to 1.0MPa.

A calcining temperature of 1800° C. or higher and a pressure of 0.7 to1.0 MPa are preferable as the condition in calcining temperature andpressure for the pressure-nitridating step.

It is because nitridation of boron carbide does not proceed sufficientlywhen the calcining temperature is 1800° C. and the pressure is less than0.7 MPa. In addition, produce at a pressure of 1.0 MPa or less isdesirable industrially.

The atmosphere in the pressure-nitridating step is desirably a gaspermitting nitridation reaction and examples thereof include nitrogengas, ammonia gas, and the like. These gases may be used alone or incombination of two or more. In particular, nitrogen gas is mostdesirable for nitridization from the point of production cost. Theatmosphere preferably contains nitrogen gas at least in an amount of 95%(V/V) or more, more preferably 99.9% or more.

The calcination period in the pressure-nitridating step is preferably 6to 30 hours, more preferably 8 to 20 hours.

<1-2. (b) Decarburization Crystallization Step>

In the “(b) decarburization crystallization step” of the method forproducing a boron nitride powder according to the present invention, itis possible to prepare boron nitride aggregated grains that are formedby aggregation of primary particles (primary particles of scalyhexagonal boron nitride) by carrying out an heat treatment of heatingthe boron carbide nitride prepared in the pressure-nitridating step to aretention temperature at a particular heating rate under an atmosphereat normal pressure or higher and heating it in a particular temperaturerange for a certain period of time.

In the decarburization crystallization step, the boron carbide nitrideprepared from boron carbide, as described above, is decarburized, grownto scaly grains having a particular size and aggregated, to giveaggregated boron nitride grains.

Preferably in the decarburization crystallization step, the boroncarbide nitride is subjected to a heat treatment of heating it to atemperature allowing initiation of decarburization in an atmosphere atnormal pressure or higher, heating it to a retention temperature at aheating rate of 5° C./min or less and heating it at a temperature of1750° C. or higher for more than 0.5 hour and less than 40 hours.

More preferably in the decarburization crystallization step, the boroncarbide nitride is subjected to a heat treatment of heating it to atemperature allowing initiation of decarburization in an atmosphere atnormal pressure or higher, heating it to a retention temperature at aheating rate of 5° C./min or less and heating it at a temperature of1800° C. or higher for 1 hour or more and 30 hours or less.

Desirably in the decarburization crystallization step, boron carbidenitride prepared in the pressure-nitridating step and boric acid and/orboron oxide (with other raw materials, as needed) are mixed as the rawmaterials in the step and the mixture is decarburized and crystallized.

The mixing rate of boric acid and/or boron oxide to the boron carbidenitride is preferably 100 to 300 parts by mass of boric acid-boronoxide, more preferably 150 to 250 parts by mass of boric acid-boronoxide, with respect to 100 parts by mass of the boron carbide nitride.

The pressure condition of the “atmosphere of normal pressure or higher”in the decarburization crystallization step is preferably normalpressure or higher, more preferably 0.1 MPa or higher, yet morepreferably 0.2 MPa or higher. The maximum allowable value of thepressure condition of the atmosphere is not particularly limited, butpreferably 1 MPa or less, more preferably 0.5 MPa or less. The pressurecondition is preferably 0.2 to 0.4 MPa.

The “atmosphere” in the decarburization crystallization step ispreferably nitrogen gas and an atmosphere containing nitrogen gas in anamount of 90% (V/V) or more is preferable and high-purity nitrogen gas(99.9% or more) is more preferable.

The “heating” in the decarburization crystallization step may beperformed in one step or in multiple steps. Multi-step heating isdesirably selected for reduction of the time needed for heating to thetemperature allowing initiation of decarburization.

In the “first-step heating” of the multi-step heating, the boron carbidenitride is preferably heated to the “temperature allowing initiation ofdecarburization”.

The “temperature allowing initiation of decarburization” is notparticularly limited and may be any temperature normally employed, andit may be, for example, approximately 800 to 1200° C. (favorably,approximately 1000° C.).

The “first-step heating” may be carried out, for example, at a heatingrate in the range of 5 to 20° C./min, favorably 8 to 12° C./min.

A second-step heating is preferably carried out after the first-stepheating. The “second-step heating” is more preferably carried out by“heating the boron carbide nitride to a desired retention temperature”.

The maximum allowable value of the “second-step heating rate” ispreferably 5° C./min or less, more preferably 4° C./min or less, morepreferably 3° C. or lower, yet more preferably 2° C. or lower. A lowerheating rate is preferable for more uniform growth of the grains.

The minimum allowable value of the “second-step heating rate” ispreferably 0.1° C./min or more, more preferably 0.5° C./min or more, yetmore preferably 1° C./min or more. A “second-step heating rate” of 1° C.or higher is preferable from the point of production cost, as it permitsreduction in production period.

The “second-step heating rate” is favorably 0.1 to 5° C./min.

A second-step heating rate of more than 5° C./min leads to heterogeneousgrowth of grains and thus production of heterogeneously structuredgrains, possibly leading to deterioration in grain strength.

The minimum allowable value of the “particular temperature range(retention temperature after heating)” is preferably 1750° C. or higher,more preferably 1800° C. or higher, yet more preferably 2000° C. orhigher. The maximum allowable value of the “retention temperature” ispreferably 2200° C. or lower, more preferably 2100° C. or lower.

A retention temperature after heating of less than 1750° C. leads toinsufficient growth of grains, possibly leading to reduction in thermalconductivity. A retention temperature of 1800° C. or higher easily leadsto favorable growth of grains, thus improving thermal conductivity.

The “certain retention period (retention period after heating)” ispreferably more than 0.5 hour and less than 40 hours.

The “retention period” is preferably 1 hour or more, more preferably 3hours or more, yet more preferably 5 hours or more, even more preferably10 hours or more.

The maximum allowable value of the “retention period” is preferably 30hours or less, more preferably 20 hours.

The retention period is desirably 1 to 30 hours.

When the retention period after heating is 1 hour or more, the grainsgrow favorably. It is possible, when it is 30 hours or less, to preventexcessive grain growth and thus deterioration in grain strength and toavoid industrial disadvantage of extended calcination period.

The boron nitride powder in the first embodiment of the presentinvention can be prepared after the (a) pressure-nitridating andcalcining step and the (b) decarburization crystallization step.

For reduction of the weak aggregation among aggregated grains, the boronnitride aggregated grains prepared in the decarburizationcrystallization step is desirably pulverized or crushed and additionallyclassified.

The pulverization or crushing is not particularly limited, and anycommon pulverizer or crusher may be used. A common sieving method givinggrains having an average particle diameter of 20 μm or more and 100 μmor less may be used for classification. For example, the lumps arepulverized in a Henschel Mixer or a mortar and then classified on avibration sieving machine.

A boron nitride powder comprising the boron nitride aggregated grainsprepared by the method for producing a boron nitride powder in the firstembodiment of the present invention is characterized in the same way asthe <1-1. the boron nitride powder in the first embodiment of thepresent invention> described above.

The boron nitride aggregated grains prepared by the method for producinga boron nitride powder in the first embodiment of the present inventionor the boron nitride powder comprising the boron nitride aggregatedgrains can be used as the raw material of the second embodiment of thepresent invention described below.

<1-3. Thermally Conductive Resin Composition>

The thermally conductive resin composition in the second embodiment ofthe present invention is characterized by comprising the boron nitridepowder in the first embodiment of the present invention or a boronnitride powder prepared by the method for producing a boron nitridepowder in the first embodiment of the present invention. Any knownproduction method may be used as the method for producing a thermallyconductive resin composition. The thermally conductive resin compositionprepared can be used widely, for example in heat-dissipating parts.

The boron nitride powder in the third embodiment described below may beused in the thermally conductive resin composition, as it is blendedwith the boron nitride powder in the first embodiment of the presentinvention, in the range that does not impair the advantageous effects ofthe present invention. The boron nitride powder according to the presentinvention can also be used as an inorganic filler for thermallyconductive resin compositions.

<Resin>

Examples of the resins used in the thermally conductive resincomposition containing the boron nitride powder according to the presentinvention include epoxy resins, silicone resins, silicone rubbers,acrylic resins, phenol resins, melamine resins, urea resins, unsaturatedpolyesters, fluoroplastics, polyamides (for example, polyimides,polyamide-imides, polyether imides), polyesters (for example,polybutylene terephthalate, polyethylene terephthalate), polyphenyleneethers, polyphenylene sulfides, wholly aromatic polyesters,polysulfones, liquid crystalline polymers, polyether sulfones,polycarbonates, maleimide-modified resins, ABS resins, AAS(acrylonitrile-acrylic rubber-styrene) resins, and AES(acrylonitrile-ethylene-propylene-diene rubber-styrene) resins.

In particular, epoxy resins (favorably, naphthalene-type epoxy resins),which are superior in heat resistance and adhesive strength to copperfoil circuits, are favorable as an insulation layer for printed wiringboards.

In addition, silicone resins, which are superior in heat resistance,softness, and adhesiveness to heat sink, and the like, are favorable asa thermal interface material.

Typical examples of the epoxy resin hardeners include phenolic novolakresins, acid anhydride resins, amino resins, and imidazoles. Among theresins above, imidazoles are preferable.

The amount of the hardener blended is preferably 0.5 part by mass ormore and 15 parts by mass or less, more preferably 1.0 part by mass ormore and 10 parts by mass or less.

The amount of the boron nitride powder used in 100 vol % of thethermally conductive resin composition (i.e., the total amount of theepoxy resin and the hardener) is preferably 30 vol % or more and 85 vol% or less, more preferably, 40 vol % or more and 80 vol % or less.

A use amount of the boron nitride powder of 30 vol % or more easilyleads to improvement in thermal conductivity and thus to sufficientlyhigh heat dissipating property. When the content of the hexagonal boronnitride is 85 vol % or less, it is possible to reduce generation ofvoids during molding and thus to reduce deterioration in insulatingproperty and mechanical strength.

Particularly preferably, the first and second embodiments of the presentinvention relates to a boron nitride powder superior in thermalconductivity to be used in the resin composition for an insulation layerand a thermal interface material of printed wiring boards, a method forproducing the same and a thermally conductive resin compositioncomprising the same.

Specifically, the first and second embodiments of the present inventionare used favorably as the raw materials for heat-dissipating parts inheat-generating electronic parts such as power devices.

The thermally conductive resin composition in the second embodiment ofthe present invention can be used widely, for example inheat-dissipating parts.

Another embodiment of the present invention relates to an aggregatedboron nitride powder, a method for producing the same, and a thermallyconductive resin composition comprising the same.

More specifically, the other embodiment of the present invention relatesto an aggregated boron nitride powder that is surface-treated and thussuperior in filling property into resin, a method for producing the sameand a thermally conductive resin composition comprising the same.

As described above, hexagonal boron nitride (hereinafter also referredto as “h-BN”) powder, which has excellent properties as an electricalinsulating material such as high thermal conductivity, high insulatingproperty, and low dielectric constant, is attracting attention.

Patent Document 1 proposes a high-heat conduction sheet in which thein-plane direction (a-axis direction) of the hexagonal boron nitrideparticles is oriented in the thickness direction of the high-heatconduction sheet.

Patent Document 2 proposes use of aggregated boron nitride powder inwhich the hexagonal boron nitride primary particles are not oriented inthe same direction.

Known aggregated boron nitrides prepared by other production methodsinclude an aggregated boron nitride prepared by providing a reducedpressure treatment of storing the raw material boron carbide under afurnace internal pressure of less than 100 kPa during nitridatingtreatment or after the decarburization treatment (Patent Document 6) andan aggregated boron nitride prepared by repeated pressurization andcrushing (Patent Document 7).

Alternatively, Patent Document 8 discloses surface treatment ofaggregated boron nitride and Patent Document 9 discloses surfacemodification for improvement in filling property by surface treatment ofboron nitride, for example, with a paint conditioner.

However, as described in Patent Document 1, as the hexagonal boronnitride particles are scaly in shape, when the hexagonal boron nitridepowder is mixed with a resin, the particles tend to orient in the samedirection. For that reason, when hexagonal boron nitride particles aremixed with a resin, the resulting resin becomes more viscous, resultingin deterioration in flowability, and it became difficult to add theparticles densely in a resin.

In addition, the aggregated boron nitrides prepared in Patent Documents2, 6, and 7 had a filling property lower than that, for example, ofaluminum oxide having the same particle diameter, and thus demandedimprovement in filling property into resin.

Although surface treatment of aggregated boron nitride is disclosed forexample in Patent Document 8, it is a so-called integral treatment, andthe surface treatment was not sufficiently effective, as the amount ofthe coupling agent that was actually consumed for coupling was lowerthan the amount of the coupling agent added.

In addition, although surface modification of boron nitride for exampleby a paint conditioner for improvement in filling property by surfacetreatment was reported in Patent Document 9, such a treatment ofconventional aggregated boron nitride powder resulted in breakdown ofaggregation and there was observed no improvement in filling propertyinto resin.

Thus, in another embodiment, a main object of the present technology isto provide an aggregated boron nitride powder that is surface-treatedand superior in filling property into resin, a method for producing thesame, and a thermally conductive resin composition comprising the same.

After intensive studies, the inventors have made the present invention.Specifically, the inventors have conducted intensive studies forimprovement in filling property into resin of the aggregated boronnitride powder. As a result, it was found that it is possible to improvethe filling property into resin of aggregated boron nitride powder byusing very a high-strength raw material aggregated boron nitride powderas raw material and applying a special surface treatment, which enablesmore effective surface treatment, to the powder. As a result, theinventors have made another embodiment of the present invention.

Another embodiment of the present invention provides an aggregated boronnitride powder having the following characteristics (A) to (D):

(A) the boron nitride aggregated grains are formed by aggregation ofhexagonal h-BN primary particles;(B) the boron nitride aggregated grains have any one or more of Si, Ti,Zr, Ce, Al, Mg, Ge, Ga, and V in an amount of 0.1 atm % or more and 3.0atm % or less in its composition on the surface of 10 nm;(C) the boron nitride aggregated grains have a crushing strength (at63.2%) of 5 MPa or more; and(D) the aggregated boron nitride powder has an average particle diameterof 20 μm or more and 100 μm or less.

The aggregated boron nitride powder may have additionally the followingcharacteristic: (E) the boron nitride aggregated grains have organicfunctional groups present on the surface.

Yet another embodiment of the present invention provides a method forproducing a surface-treated aggregated boron nitride powder, comprisingadding an oxidizer to a raw material bulky boron particles having anaverage particle diameter of 20 μm or more and 100 μm or less and acrushing strength (at 63.2%) of 10 MPa or more, allowing surfacemodification treatment of the particles by wet-pulverization orwet-crushing, and additionally allowing reaction of the particle with ametal coupling agent.

A method for producing a surface-treated aggregated boron nitride powderin yet another embodiment of the present invention is a method whereinan oxidizer and a water-soluble solvent can be added during the surfacemodification treatment.

In the method for producing a surface-treated aggregated boron nitridepowder described above, the metal coupling agent may be one or moreagents selected from titanium coupling agents, silane coupling agents,zirconium coupling agents, and aluminum coupling agents.

Yet another embodiment of the present invention provides a method forproducing a surface-modified aggregated boron nitride powder comprisingadding an oxidizer to a raw material aggregated boron nitride powderhaving an average particle diameter of 20 μm or more and 100 μm or lessand a crushing strength (at 63.2%) of 10 MPa or more, allowing surfacemodification treatment of the particles by wet-pulverization orwet-crushing of the mixture.

It also provides a surface-modified aggregated boron nitride powderprepared by the method for producing a surface-modified aggregated boronnitride powder described above.

It also provides a thermally conductive resin composition comprising theaggregated boron nitride powder.

The present technology provides an aggregated boron nitride powdersuperior in filling property into resin, a method for producing thesame, and a thermally conductive resin composition comprising the same.

<2-1. Aggregated Boron Nitride Fine Powder in the Third Embodiment ofthe Present Invention>

The aggregated boron nitride powder in the third embodiment of thepresent invention has the characteristics (A) to (D) below. Theaggregated boron nitride powder in the third embodiment of the presentinvention is superior in filling property into resin.

(A) The boron nitride aggregated grains are formed by aggregation ofhexagonal h-BN primary particles;(B) the boron nitride aggregated grains have any one or more of Si, Ti,Zr, Ce, Al, Mg, Ge, Ga, and V in an amount of 0.1 atm % or more and 3.0atm % or less in its composition on the surface of 10 nm;(C) The boron nitride aggregated grains have a crushing strength of 5MPa or more; and(D) The aggregated boron nitride powder has an average particle diameterof 20 μm or more and 100 μm or less.

The aggregated boron nitride powder in the third embodiment of thepresent invention is characterized in that “(A) the boron nitrideaggregated grains are formed by aggregation of hexagonal h-BN primaryparticles”.

The aggregated boron nitride powder in the third embodiment of thepresent invention is a powder comprising boron nitride aggregated grainssurface-treated with a metal coupling agent.

The surface-treated boron nitride aggregated grains can be prepared byusing, as the raw material, an aggregated boron nitride powdercontaining boron nitride aggregated grains having a particular crushingstrength that are formed by aggregation of hexagonal h-BN primaryparticles. The raw material boron nitride aggregated grains formed byaggregation of hexagonal h-BN primary particles can be prepared in the<(a) pressure-nitridating and calcining step> and the <(b)decarburization crystallization step> described below.

The shape of the “hexagonal h-BN primary particles” in the thirdembodiment of the present invention is preferably scaly.

The size, i.e., the average long side length of primary particles, ofthe “hexagonal h-BN primary particles” in the third embodiment of thepresent invention is preferably 1.5 to 3.5 μm, more preferably 1.7 to3.2 μm, more preferably 2.0 to 3.0 μm.

When the average long side length of the primary particles is more than3.5 μm, aggregated grains formed by aggregation of primary particleshave a coarse structure internally, possibly leading to deterioration ingrain strength. An average long side length of the primary particles ofless than 1.5 μm may lead to deterioration in thermal conductivity, asthe primary particles are smaller.

The “hexagonal h-BN primary particles” in the third embodiment of thepresent invention preferably have a standard deviation of the long sidelength of primary particles at 0.2 to 1.2 μm, more preferably 0.4 to 1.0μm, yet more preferably 0.8 μm or less.

A standard deviation of more than 1.2 μm may give particles having anuneven structure with reduced grain strength. The minimum allowablevalue of the standard deviation of the long side length of primaryparticles is not particularly limited, but a standard deviation of lessthan 0.2 μm may give particles that are excessively uniform and have adense structure, which are resistant to resin penetration and cause forexample generation of voids, possibly leading to deterioration indielectric breakdown properties.

The aggregated boron nitride powder in the third embodiment of thepresent invention is characterized in that “(B) the boron nitrideaggregated grains have any one or more of Si, Ti, Zr, Ce, Al, Mg, Ge,Ga, and V in an amount of 0.1 atm % or more and 3.0 atm % or less in itscomposition on the surface of 10 nm”, as described in the thirdembodiment of the present invention.

In “the composition on the surface of 10 nm of the boron nitrideaggregated grains” in the third embodiment of the present invention, ametal element in an amount of less than 0.1 atm % may lead toinsufficient improvement effect in filling property and use of a fillercontaining a metal element in an amount of more than 3.0 atm % mayresult in deterioration in thermal conductivity.

In the composition on the surface of 10 nm of the boron nitrideaggregated grains in the third embodiment of the present invention, anyone or more of Si, Ti, Zr, and Al is preferably present in an amount of0.1 atm % or more and 3.0 atm % or less.

The aggregated boron nitride powder in the third embodiment of thepresent invention is characterized in that “(C) the boron nitrideaggregated grains have a crushing strength of 5 MPa or more”, asdescribed in the third embodiment of the present invention. The“crushing strength” or the “crushing strength (at 63.2%)” is alsoreferred to as “grain strength (at a cumulative breakdown rate of63.2%)”.

The “crushing strength of boron nitride aggregated grains” in the thirdembodiment of the present invention is preferably 5 MPa or more, morepreferably 6 MPa or more. When the grain strength (at 63.2%) is lessthan 5 MPa, aggregation may be disintegrated during kneading with aresin, leading to deterioration in thermal conductivity and fillingproperty. The maximum allowable value of the “crushing strength of boronnitride aggregated grains” in the third embodiment of the presentinvention is not particularly limited, and may be, for example, 30 MPa,20 MPa, or 10 MPa.

The aggregated boron nitride powder in the third embodiment of thepresent invention is characterized in that “(D) the aggregated boronnitride powder has an average particle diameter of 20 μm or more and 100μm or less”, as described in the third embodiment of the presentinvention.

The “average particle diameter of the aggregated boron nitride powder”in the third embodiment of the present invention is preferably 20 μm ormore, more preferably 22 μm or more, yet more preferably 30 μm or more.The average particle diameter of the aggregated boron nitride powder ispreferably 100 μm or less, more preferably 90 μm or less, yet morepreferably 80 μm or less.

An average particle diameter of less than 20 μm, which is significantlysmall, may lead to decrease in thermal conductivity. Alternatively whenthe average particle diameter is more than 100 μm, there is a smallerdifference between the average particle diameter of the boron nitridepowder and the thickness of the heat dissipation sheet and thus, it maybecome harder to produce the sheet.

In the third embodiment of the present invention, an aggregated boronnitride powder having an average boron nitride powder diameter of 20 μmor more and 100 μm or less and a crushing strength of 6 MPa or more ispreferable. An aggregated boron nitride powder having an average boronnitride powder diameter of 30 μm or more and 80 μm or less is morepreferable.

The aggregated boron nitride powder in the third embodiment of thepresent invention is further characterized in that “(E) the boronnitride aggregated grains have organic functional groups present on thesurface”, as described in the third embodiment of the present invention.

Examples of the organic functional groups present on the surface of theboron nitride aggregated grains include epoxy groups that may besubstituted, styryl groups that may be substituted, alkyl groups thatmay be substituted, vinyl groups that may be substituted, acetylacetategroups that may be substituted, acyl groups that may be substituted,isocyanate groups that may be substituted, cyclohexyl groups that may besubstituted, and tetraoctyl bis(ditridecyl phosphite) groups that may besubstituted. The organic functional group may be a substituted orunsubstituted organic functional group. The organic functional group isone or more groups selected from these groups.

The epoxy group that may be substituted is, for example, an epoxy group.

The aryl group that may be substituted is, for example, a styryl groupthat may be substituted.

Examples of the alkyl groups that may be substituted include propylgroups that may be substituted (for example, methacryloxypropyl group,acryloxypropyl group, aminoethylaminopropyl group, glycidoxypropylgroup, phenylaminopropyl group), and alkyl groups having astraight-chain carbon number of 5 or more (favorably, straight-chaincarbon number of 5 to 25).

The vinyl group that may be substituted is, for example, a vinyl group,a styryl group, an acetylacetonate group, or a methacryloyl group.

The acetylacetonate group that may be substituted is, for example, anacetylacetonate group.

The acyl group that may be substituted is, for example, anacetylacetonate group, an isopropyl triisostearoyl group, a methacrylgroup, or a methacryloyl group.

The isocyanate group that may be substituted is, for example, anisocyanate group.

The cyclohexyl group that may be substituted is, for example, acyclohexyl group.

The tetraoctyl bis(ditridecylphosphite) group that may be substitutedis, for example, a tetraoctyl bis(ditridecylphosphite) group.

The organic functional group may be one or more selected from thesegroups.

Examples of the organic functional groups present on the surface of theaggregated boron nitride powder include epoxy groups, styryl groups,methacryloxypropyl group, an acryloxypropyl group, anaminoethylaminopropyl group, glycidoxypropyl group, a phenylaminopropylgroup, acetylacetonate groups, vinyl groups, methacryl groups,methacryloyl groups, an isopropyl triisostearoyl group, an tetraoctylbis(ditridecyl phosphite) group, cyclohexyl groups, isocyanate groups,and alkyl groups having a straight-chain carbon number of 5 or more. Theorganic functional group may be one or more selected from these groups.

Among the groups above, an epoxy group, a styryl group, aglycidoxypropyl group, an acetylacetonate group, a vinyl group,isopropyltriisostearoyl group, a tetraoctyl bis(ditridecyl phosphite)group, a cyclohexyl group, or an isocyanate group is more favorable.

The organic functional group may be one or more selected from thesegroups.

<2-2. Method for Producing a Surface-Treated Aggregated Boron NitridePowder According to the Present Invention>

The method for producing a surface-treated aggregated boron nitridepowder in the third embodiment of the present invention comprises (1)preparing an aggregated boron nitride powder containing the raw materialhigh-strength boron nitride aggregated grains (hereinafter, alsoreferred to as “the first aggregated boron nitride powder”) and (2)allowing a special surface modification treatment of the aggregatedboron nitride powder (raw material) and a metal coupling reaction of theresulting powder.

It is possible in this way to prepare the surface-treated aggregatedboron nitride powder in the third embodiment of the present invention(hereinafter, also referred to as “second aggregated boron nitridepowder”).

<Aggregated Boron Nitride Powder (First Aggregated Boron Nitride Powder)Used as the Raw Material in the Third Embodiment of the PresentInvention>

The aggregated boron nitride powder used as the raw material in thethird embodiment of the present invention should be extremely high ingrain strength and is preferably prepared, for example, by theproduction method described below. The production method below give, forexample, a boron nitride powder shown in FIGS. 1 to 3. The boron nitridepowder in the first embodiment or a boron nitride powder prepared by themethod for producing a boron nitride powder in the first embodimentdescribed above can be used as the raw material.

The aggregated boron nitride powder used as the raw material in thethird embodiment of the present invention can be prepared by (a)pressure-nitridating and calcining boron carbide and (b) decarburizingand crystallizing the boron carbide after calcination.

The method for producing an aggregated boron nitride powder used as theraw material in the third embodiment of the present invention comprisesthe following steps (a) and (b) of (a) pressure-nitridating andcalcining a boron carbide having an average particle diameter of 6 μm ormore and 55 μm or less, and

(b) heating the boron carbide to a temperature allowing initiation ofdecarburization, heating it to a retention temperature at a heating rateof less than 5° C./min, and subjecting the boron carbide to a heattreatment of storing it at a temperature of 1750° C. or higher for morethan 0.5 hour and less than 20 hours, in a decarburizationcrystallization step after pressure nitridation and calcination.

<2-2. (a) Pressure-Nitridating and Calcining Step>

In the “(a) pressure-nitridating step” in the method for producing aboron nitride powder that is used as the raw material in the thirdembodiment of the present invention, boron carbide having an averageparticle diameter of 6 μm or more and 55 μm or less ispressure-nitridated and calcined in an atmosphere at a particularcalcining temperature under a particular applied pressure condition, togive a boron carbide nitride.

<2-2. (a1) Boron Carbide>

The minimum allowable value of the average particle diameter of theboron carbide is preferably 6 μm or more, more preferably 7 μm or more,yet more preferably 10 μm or more.

The maximum allowable value of the average particle diameter of theboron carbide is preferably 55 μm or less, more preferably 50 μm orless, yet more preferably 45 μm or less.

The average particle diameter of the boron carbide is preferably 7 to 50μm, more preferably 7 to 45 μm.

The boron carbide preferably has a carbon content of 18.0% to 20.5%.

Any production method may be used as the method for producing the boroncarbide and gives a boron carbide having a desired average particlediameter and a carbon content.

It is possible to obtain boron carbide lumps, for example, by mixingboric acid and acetylene black and heating the mixture in an atmosphereat 1800 to 2400° C. for 1 to 10 hours. The lumps may, for example, bepulverized, sieved, washed, purified, and dried, as needed, to give aboron carbide powder.

Boric acid and acetylene black, raw materials of boron carbide, arefavorably mixed at a ratio of 25 to 40 parts by mass of acetylene blackto 100 parts by mass of boric acid.

The atmosphere in which the boron carbide is produced is preferably aninert gas, and examples of the inert gases include argon gas andnitrogen gas. These gases may be used alone or in combination. Inparticular, argon gas is preferable.

A common pulverizer or crusher can be used for pulverization of theboron carbide lumps and the lumps are pulverized, for example, for 0.5to 3 hours.

The boron carbide after pulverization is preferably sieved with a sievescreen into particles having a particle diameter of 75 μm or less.

<2-2. (a2) Pressure-Nitridating and Calcining Step>

The minimum allowable value of the calcining temperature in thepressure-nitridating step is preferably 1700° C. or higher, morepreferably 1800° C. or higher. The maximum allowable value of thecalcining temperature is preferably 2400° C. or lower, more preferably2200° C. or lower. The calcining temperature is more preferably 1800 to2200° C.

The minimum allowable value of the pressure in the pressure-nitridatingstep is preferably 0.6 MPa or more, more preferably 0.7 MPa or more. Themaximum allowable value of the pressure is preferably 1.0 MPa or less,more preferably 0.9 MPa or less. The pressure is more preferably 0.7 to1.0 MPa.

The calcining temperature and the pressure condition in thepressure-nitridating step are preferably a calcining temperature of1800° C. or higher and a pressure of 0.7 to 1.0 MPa.

It is because nitridation of boron carbide does not proceed sufficientlywhen the calcining temperature is 1800° C. and the pressure is less than0.7 MPa. It is also desirable industrially to produce the boron carbidenitride at a pressure of 1.0 MPa or less.

The atmosphere in the pressure-nitridating step is desirably a gaspermitting the nitridation reaction and examples thereof includenitrogen gas and ammonia gas. These gases may be used alone or incombination of two or more. In particular, nitrogen gas is mostdesirable for nitridization from the point of production cost. Theatmosphere preferably contains nitrogen gas at least in an amount of 95%(V/V) or more, more preferably 99.9% or more.

The calcination period in the pressure-nitridating step is preferably 6to 30 hours, more preferably 8 to 20 hours.

<2-2. (b) Decarburization Crystallization Step>

In the “(b) decarburization crystallization step” of the method forproducing a boron nitride powder that is used as the raw material in thethird embodiment of the present invention, it is possible to prepareboron nitride aggregated grains that are formed by aggregation ofprimary particles (primary particles of scaly hexagonal boron nitride)by subjecting the boron carbide nitride prepared in thepressure-nitridating step to an heat treatment of heating it to aretention temperature at a particular heating rate under an atmosphereat normal pressure or higher and heating it at a particular temperaturerange for a certain period of time.

In the decarburization crystallization step, the boron carbide nitrideprepared from boron carbide, as described above, is decarburized, grownand aggregated to scaly grains having a particular size, to giveaggregated boron nitride grains.

Preferably in the decarburization crystallization step, the boroncarbide nitride is subjected to a heat treatment of heating it to atemperature allowing initiation of decarburization in an atmosphere atnormal pressure or higher, heating it to a retention temperature at aheating rate of less than 5° C./min, and heating it at a temperature of1750° C. or higher for more than 0.5 hour and less than 20 hours.

More preferably in the decarburization crystallization step, the boroncarbide nitride is subjected to a heat treatment of heating it to atemperature allowing initiation of decarburization in an atmosphere atnormal pressure or higher, heating it to a retention temperature at aheating rate of less than 5° C./min and heating it at a temperature of1800° C. or higher for 1 hour or more and 20 hours or less.

Desirably in the decarburization crystallization step, the boron carbidenitride prepared in the pressure-nitridating step and boric acid and/orboron oxide (with other raw materials, as needed) are mixed as the rawmaterials in the step, and the mixture is decarburized and crystallized.

The mixing rate of the boron carbide nitride with boric acid and/orboron oxide is preferably 100 to 300 parts by mass of boric acid-boronoxide, more preferably 150 to 250 parts by mass of boric acid-boronoxide, with respect to 100 parts by mass of the boron carbide nitride.

The pressure condition of the “atmosphere at normal pressure or higher”in the decarburization crystallization step is preferably normalpressure or higher, more preferably 0.1 MPa or higher, more preferably0.2 MPa or higher. The maximum allowable value of the pressure conditionof the atmosphere is not particularly limited, but preferably 1 MPa orless, more preferably 0.5 MPa or less. The pressure condition ispreferably 0.2 to 0.4 MPa.

The “atmosphere” in the decarburization crystallization step ispreferably nitrogen gas and nitrogen gas is preferably contained in theatmosphere in an amount of 90% (V/V) or more, and more preferably, highpurity nitrogen gas (99.9% or more) is used.

The “heating” in the decarburization crystallization step may beperformed in one step or in multiple steps. Multi-step heating isdesirably selected for reduction of the time needed for heating to atemperature allowing initiation of decarburization.

In the “first-step heating” of the multi-step heating the boron carbidenitride mixture is preferably heated to a “temperature allowinginitiation of decarburization”.

The “temperature allowing initiation of decarburization” is notparticularly limited and may be any temperature normally employed, andit may be, for example, approximately 800 to 1200° C. (favorably,approximately 1000° C.).

The “first-step heating” may be carried out, for example, at a heatingrate in the range of 5 to 20° C./min, favorably 8 to 12° C./min.

A second-step heating is preferably carried out after the first-stepheating. The “second-step heating” is more preferably carried out by“heating the boron carbide nitride mixture to a desired retentiontemperature”.

The maximum allowable value of the “second-step heating rate” ispreferably less than 5° C./min, more preferably 4° C./min or less, yetmore preferably 3° C. or lower, even more preferably 2° C. or lower. Alower heating rate is preferable for more uniform growth of the grains.

The minimum allowable value of the “second-step heating rate” ispreferably 0.1° C./min or more, more preferably 0.5° C./min or more, yetmore preferably 1° C./min or more. A “second-step heating rate” of 1° C.or higher is preferable from the point of production cost, as it permitsreduction in production period.

The “second-step heating rate” is favorably 0.1 to 5° C./min. Asecond-step heating rate of more than 5° C./min leads to heterogeneousgrowth of grains and thus production of heterogeneously structuredgrains, possibly leading to deterioration in grain strength.

The minimum allowable value of the “particular temperature range(retention temperature after heating)” is preferably 1750° C. or higher,more preferably 1800° C. or higher, yet more preferably 2000° C. orhigher. The maximum allowable value of the “retention temperature” ispreferably 2200° C. or lower, more preferably 2100° C. or lower.

A retention temperature after heating of less than 1750° C. leads toinsufficient growth of grains, possibly leading to deterioration inthermal conductivity. A retention temperature of 1800° C. or highereasily leads to favorable growth of grains and thus to improvement inthermal conductivity.

The “retention period (at the retention temperature after heating)” ispreferably more than 0.5 hour and less than 20 hours.

The “retention period” is preferably 1 hour or more, more preferably 3hours or more, yet more preferably 5 hours or more, even more preferably10 hours or more.

The maximum allowable value of the “retention period” is preferably 20hours or less, more preferably 15 hours or less.

The retention period is desirably 1 to 20 hours.

When the retention period after heating is 1 hour or more, the grainsgrow favorably, and when it is 20 hours or less, the grains growfavorably without deterioration in grain strength due to excessivegrowth of grains and such a retention period is also favorable forpreventing industrial disadvantage caused by extended calcinationperiod.

The boron nitride powder according to the present invention can beprepared after the pressure-nitridating and calcining step (a) and thedecarburization crystallization step (b).

For reduction of the weak aggregation among aggregated grains, the boronnitride aggregated grains prepared in the decarburizationcrystallization step is desirably pulverized or crushed and additionallyclassified.

Means for pulverization and crushing are not particularly limited, andany common pulverizer or crusher may be used. A common sieving methodthat gives grains having an average particle diameter of 20 μm or moreand 100 μm or less may be used for classification. For example, theaggregated grains are pulverized in a Henschel Mixer or a mortar andthen classified on a vibration sieving machine.

The average particle diameter of “the first aggregated boron nitridepowder” in the third embodiment of the present invention is preferably20 μm or more, more preferably 22 μm or more, yet more preferably 30 μmor more. The average particle diameter of the boron nitride powder ispreferably 100 μm or less, more preferably 90 μm or less, yet morepreferably 80 μm or less.

The average particle diameter of “the first boron nitride powder” ispreferably 20 μm or more and 100 μm or less, more preferably 30 μm ormore and 80 μm or less.

An average particle diameter of less than 20 μm may lead todeterioration in thermal conductivity, as the average particle diameteris excessively small. When the average particle diameter is more than100 μm, there is a smaller difference between the average particlediameter of the boron nitride powder and the thickness of the heatdissipation sheet, possibly making it difficult to prepare the sheet.

The grain strength (at a cumulative breakdown rate of 63.2%) of “thefirst aggregated boron nitride powder” used in the third embodiment ofthe present invention is preferably 9 MPa or more, more preferably 10MPa or more, yet more preferably 15 MPa or more, even more preferably 20MPa or more.

When the grain strength is less than 9 MPa, the aggregation may bedisintegrated during kneading with a resin, leading to deterioration inthermal conductivity and filling property.

The maximum allowable value of the grain strength (at a cumulativebreakdown rate of 63.2%) of “the first aggregated boron nitride powder”is not particularly limited, but may be, for example, 50 MPa, 40 MPa or30 MPa.

The grain strength (at a cumulative breakdown rate of 20.0%) of “thefirst aggregated boron nitride powder” used as the raw material in thethird embodiment of the present invention is more preferably 4.5 MPa ormore, more preferably 5.0 MPa or more. The maximum allowable value ofgrain strength (at a cumulative breakdown rate of 20.0%) of “the firstaggregated boron nitride powder” is not particularly limited, but maybe, for example, 20 MPa or 13 MPa.

The “average long side length of the primary particles” and the“standard deviation of the long side lengths of the primary particles”in the “scaly hexagonal boron nitride (primary particles)” of the “firstaggregated boron nitride powder” used as the raw material in the thirdembodiment of the present invention are those for the “hexagonal boronnitride h-BN primary particles” described above.

<Surface-Treated Aggregated Boron Nitride Powder in the Third Embodimentof the Present Invention (Second Aggregated Boron Nitride Powder)>

The surface treatment method used in the third embodiment of the presentinvention preferably comprises steps of (c) adding an oxidizer to thefirst aggregated boron nitride powder (raw material) andsurface-modifying the particles while wet, and additionally (d)subjecting the powder after the surface modification treatment to areaction with a metal coupling agent. It is thus possible to prepare asurface-treated aggregated boron nitride powder (second aggregated boronnitride powder).

The raw material to be surface-treated is desirably an aggregated boronnitride powder (first aggregated boron nitride powder) having an averageparticle diameter of 20 μm or more and 100 μm or less and a crushingstrength (grain strength (at a cumulative breakdown rate of 63.2%)) of10 MPa or more.

When the crushing strength (at 63.2%) of the raw material is less than10 MPa, the aggregated grains may be disintegrated during the surfacemodification treatment in a pulverizer or crusher, prohibitingpreservation of the aggregation structure. As a result, it may result indeterioration in thermal conductivity and filling property.

During the surface modification treatment, the particles are preferablysubjected to surface modification treatment while wet in a pulverizer orcrusher, as an oxidizer is added thereto.

In the metal coupling reaction, it is desirable to make thesurface-treated powder react with a metal coupling agent containing, forexample, a metal alkoxide, a metal chelate, or a metal halide.

<2-2. (c) Surface Modification Treatment Step>

The surface treatment method used in the third embodiment of the presentinvention preferably comprises a step of adding an oxidizer to the“first aggregated boron nitride powder” and subjecting the mixture to aparticle surface modification treatment while wet.

Combined use of an oxidizer in the pulverization-crushing treatmentpermits efficient modification of the particle surface and efficientprogress of the coupling reaction, as it improves dispersibility andincreases the number of surface functional groups. It is thus possibleto prepare surface-modified boron nitride aggregated grains beforetreatment with a metal coupling agent. The state of the surface-modifiedparticles is not particularly limited and may be a slurry or a powder.

The oxidizer used is not particularly limited, and examples thereofinclude hydrogen peroxides, nitric acids, and permanganic acid salts.Among the oxidizers above, those soluble in solvent and easily removableafter treatment are desirable. More desirable are hydrogen peroxides,compounds that have an oxidative force not lower than hydrogen peroxideand are soluble in solvent and easily removable after treatment (e.g.,nitric acids) and the like. These oxidizers may be used alone or incombination of two or more. Only water is desirably used as the solvent,depending on the oxidizer selected.

Combined use of the pulverization-crushing treatment and an oxidizerresults in more efficiently surface modification, improvement indispersibility, increase in the number of surface functional groups andefficient progress of the coupling reaction.

The amount of the oxidizer used is preferably 30 to 200 parts, morepreferably 50 to 150 parts, with respect to 100 parts of boron nitride.

The solvent to be mixed with the oxidizer is preferably a water-solublesolvent. The water-soluble solvents are, for example, one or moresolvents selected from water, alcohols, and dioxanes. Use of waterand/or an alcohol is preferable. The alcohol is preferably an alcoholhaving a straight-chain or branched-chain alkyl group, and those havingan alkyl group of 1 to 3 carbon atoms (e.g., methanol, ethanol, propylalcohol, isopropyl alcohol) are preferable. More preferable are water,an alcohol having 1 to 3 carbon atoms, and the mixture thereof.

The blending ratio of the oxidizer to the solvent is preferably 1 to 10parts, more preferably 2 to 7 parts, with respect to 100 parts of thesolvent.

A known wet-processable pulverizer or crusher may be used forwet-pulverization or wet-crushing in the third embodiment of the presentinvention.

The pulverizer or crusher is not particularly limited and may be anymill that permits surface modification treatment while wet such as arocking mill, a bead mill, a ball mill, a Henschel Mixer, a jet mill, astar-burst mill, or paint conditioner.

The treatment period in the pulverizer or crusher is desirably 10minutes or more and 5 hours or less. A treatment period of less than 10minutes may lead to insufficient surface modification efficiency of thepulverization or crushing and a treatment period of more than 5 hours isalso unfavorable, as it leads to deterioration in productivity and alsoin grain strength.

<2-2. (d) Step of Introducing Metal Elements and Organic FunctionalGroups>

The surface treatment method used in the third embodiment of the presentinvention preferably comprises a “step (d) of making the surface of theboron nitride aggregated grains subjected to the special surfacemodification treatment react with a metal coupling agent having organicfunctional groups”.

It is thus possible to obtain an aggregated boron nitride powder in thethird embodiment of the present invention (also referred to as “secondaggregated boron nitride powder” or “surface-treated aggregated boronnitride powder”) that have metal elements and organic functional groupspresent on the particle surface of the boron nitride powder.

The aggregated boron nitride powder in the third embodiment of thepresent invention contains the surface-treated boron nitride aggregatedgrains.

It is desirable, before the metal coupling reaction, to filter and washthe slurry obtained by sieving the boron nitride particles afterparticle surface modification treatment. The washing liquid is notparticularly limited and, for example, a solvent that is miscible withoxidizer may be used.

The temperature of the coupling reaction condition is preferably 10 to70° C., more preferably 20 to 70° C.

The period of the coupling reaction condition is preferably 0.2 to 5hours, more preferably 0.5 to 3 hours.

The solvent for the metal coupling reaction is not particularly limitedand examples thereof include alcohols (favorably, straight- orbranched-chain alcohols having 1 to 5 carbon atoms), acetone, and furan.Among the solvents above, methanol, ethanol, propyl alcohol, isopropylalcohol, and acetone are preferable. These solvents may be used alone orin combination of two or more.

The amount of the solvent used for the metal coupling reaction ispreferably 100 to 2000 parts, more preferably 600 to 1200 parts, withrespect to 100 parts of boron nitride.

The amount of the metal coupling agent used is not particularly limitedand preferably 0.5 to 10 parts, more preferably 1 to 5 parts, withrespect to 100 parts of boron nitride.

In the present invention, the metal coupling agent is not particularlylimited. As shown in [Examples] below, it was possible to bind an metalelement and organic functional groups onto the surface of the boronnitride aggregated grains using various metal coupling agents and thusin the present invention, a desired metal coupling agent may be used asproperly selected.

It is preferable to select a coupling agent that is suited for the resinused. It is possible in this way to obtain an aggregated boron nitridepowder that is favorably compatible with the resin used in the thermallyconductive resin composition.

Examples of the metal coupling agents used in the third embodiment ofthe present invention include, but are not limited to, metal couplingagents, such as metal alkoxides, metal chelates, and metal halides,containing Si, Ti, Zr, or Al and a coupling agent suitable for the resinused is preferably selected.

If the metal coupling agent contains a straight-chain alkyl group forintroduction, the alkyl group preferably has a carbon number of 5 ormore.

The coupling agent is preferably added in such an amount that theaggregated boron nitride powder according to the present inventioncontains any one of Si, Ti, Zr and Al in an amount of 0.1 atm % or moreand 3.0 atm % or less, as determined by X-Ray photoelectron spectroscopyanalysis, in its composition on the surface of 10 nm. When the treatmentamount is less than 0.1 atm %, there may be insufficient improvementeffect in filling property, and when it is more than 3.0 atm %, it mayresult in deterioration in the thermal conductivity when the powder isused as a filler.

Examples of the titanium coupling agents include isopropyltriisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate,isopropyl tris(dioctylpyrophosphate) titanate, tetraisopropylbis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecylphosphite)titanate, tetra(2,2-diallyloxymethyl) bis(ditridecyl)phosphite titanate,bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyltri(dioctylphosphate) titanate, isopropyl tricumylphenyl titanate,isopropyl tri(N-aminoethyl-aminoethyl) titanate, dicumylphenyloxyacetatetitanate, and diisostearoyl ethylene titanate.

Preferable among the compounds above are isopropyl triisostearoyltitanate (metal alkoxide), tetraisopropyl bis(dioctylphosphite) titanate(metal chelate), and tetraoctyl bis(ditridecylphosphite) titanate (metalchelate).

Examples of the silane coupling agents include vinylsilanes such asvinyl trichlorosilane, vinyl tris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane;γ-methacryloxypropyltrimethoxysilane; epoxysilanes such asβ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane; and aminosilanes such asN-β-(aminoethyl)-γ-aminopropyltrimethoxysilane,N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane,γ-aminopropyltrimethoxysilane, andN-phenyl-γ-aminopropyltrimethoxysilane. Other silane coupling agentsinclude γ-mercaptopropyltrimethoxysilane,γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, and the like.

Preferable among them are 3-glycidyloxypropyltrimethoxysilane,p-styryltrimethoxysilane (metal alkoxide),3-isocyanatopropyltriethoxysilane (metal alkoxide),vinyltrimethoxysilane (metal alkoxide), andcyclohexylmethyldimethoxysilane (metal alkoxide).

Examples of the zirconium coupling agents includetetra-n-propoxyzirconium, tetra-butoxyzirconium, zirconiumtetraacetylacetonate, zirconium dibutoxybis(acetylacetonate), zirconiumtributoxyethylacetoacetate, zirconium butoxyacetylacetonate bis(ethylacetoacetate), and tetrakis(2,4-pentanedionato)zirconium.

Preferable among them are tetrakis(2,4-pentanedionato)zirconium (metalalkoxide).

Examples of the aluminum coupling agents include aluminum isopropylate,mono-sec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminumethylate, ethyl acetoacetate aluminum diisopropylate, aluminumtris(ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate,aluminum monoacetylacetonate bis(ethyl acetoacetate), aluminumtris(acetyl acetoacetate), and aluminum bisethyl acetoacetatemonoacetylacetonate.

Preferable among them is aluminum bisethylacetoacetate-monoacetylacetonate (metal chelate compound).

The aggregated boron nitride powder according to the present invention(second aggregated boron nitride powder) prepared by the method forproducing a boron nitride powder in the third embodiment of the presentinvention is characterized in a similar manner to <2-1. The aggregatedboron nitride fine powder in the third embodiment of the presentinvention> described above.

<2-3. Thermally Conductive Resin Composition>

The thermally conductive resin composition in the fourth embodiment ofthe present invention is characterized by containing the aggregatedboron nitride powder in the third embodiment of the present invention oran aggregated boron nitride powder prepared by the production method inthe third embodiment of the present invention described above. A knownproduction method may be used as the method for producing the thermallyconductive resin composition. The thermally conductive resin compositionprepared can be used widely, for example as a heat-dissipating part.

It is preferable to use an aggregated boron nitride powder in the thirdembodiment of the present invention that is higher in compatibility withthe resin used as the raw material. As the aggregated boron nitridepowder in the third embodiment of the present invention has organicfunctional groups present on the particle surface, it is preferable toselect and produce a favorable aggregated boron nitride powder, as thecompatibility between the organic functional groups and the raw materialresin is taken into consideration.

The aggregated boron nitride powder in the third embodiment of thepresent invention can, as it suppresses increase in viscosity when thethermally conductive resin composition is prepared, be applicable to ahigh-viscosity raw material resin. As described above, the aggregatedboron nitride powder in the third embodiment of the present inventioncan be applicable to a wide variety of raw material resins.

The boron nitride powder in the first embodiment described above may beused in a thermally conductive resin composition, as it is blended withthe boron nitride powder in the third embodiment of the presentinvention in the range that does not impair the advantageous effects ofthe present invention. The boron nitride powder according to the presentinvention can also be used as an inorganic filler in thermallyconductive resin compositions.

<Resin>

Examples of the resins used in the thermally conductive resincomposition containing the aggregated boron nitride powder in the thirdembodiment of the present invention include epoxy resins, siliconeresins, silicone rubbers, acrylic resins, phenol resins, melamineresins, urea resins, unsaturated polyesters, fluoroplastics, polyamides(for example, polyimides, polyamide-imides, polyether imides),polyesters (for example, polybutylene terephthalate, polyethyleneterephthalate), polyphenylene ethers, polyphenylene sulfides, whollyaromatic polyesters, polysulfones, liquid crystalline polymers,polyether sulfones, polycarbonates, maleimide-modified resins, ABSresins, AAS (acrylonitrile-acrylic rubber-styrene) resins, and AES(acrylonitrile-ethylene-propylene-diene rubber-styrene) resins.

In particular, epoxy resins (favorably, bisphenol A-type epoxy resins,naphthalene-type epoxy resins, etc.), which are superior in heatresistance and adhesive strength to copper foil circuits, are favorableas an insulation layer for printed wiring boards.

Silicone resins, which are superior in heat resistance, flexibility, andadhesiveness for example to heat sink, are favorable as a thermalinterface material.

Typical examples of the epoxy resin hardeners include phenolic novolakresins, acid anhydride resins, amino resins, and imidazoles. Among theresins above, imidazoles are preferable.

The amount of the hardener blended is preferably 0.5 part by mass ormore and 15 parts by mass or less, more preferably 1.0 part by mass ormore and 10 parts by mass or less.

The amount of the aggregated boron nitride powder used in 100 vol % ofthe thermally conductive resin composition is preferably 30 vol % ormore and 85 vol % or less, more preferably 40 vol % or more and 80 vol %or less, with respect to the total amount of epoxy resin and hardener.

When the amount of the aggregated boron nitride powder used is 30 vol %or more, the thermally conductive resin composition has improved thermalconductivity and easily shows sufficiently high heat dissipatingperformance. When the content of the aggregated boron nitride powder is85 vol % or less, it is possible to reduce void generation duringmolding and thus to reduce deterioration in insulating efficiency andmechanical strength of the molded product.

The surface-treated aggregated boron nitride powder in anotherembodiment of the present invention can be used widely, for example as aheat-dissipating part.

Various test methods employed include the followings:

(1) Average Particle Diameter

A laser diffraction/scattering particle size distribution analyzer(LS-13 320) manufactured by Beckmann Coulter was used for measurement ofthe average particle diameter. The average particle diameter obtainedwithout pretreatment in a homogenizer before measurement was used as theaverage particle diameter. The average particle diameter obtained is avolume-based average particle diameter.

(2) Grain Strength

Grain strength was determined according to JIS R1639-5. The analyzerused was a micro-compression testing machine (“MCT-W500”, manufacturedby Shimadzu Corporation). The grain strength (σ:MPa) was determined froma dimensionless number that changes according to the position in thegrain (α=2.48: −), a crushing test force (P:N), and a particle diameter(d:μm) according to the following formula: σ=α×D/(π×d2). Twenty or moreparticles were analyzed and the values at cumulative breakdown rates of20% and/or 63.2% were determined. The value at a cumulative breakdownrate of 63.2% was used as the grain strength (crushing strength) inTables 3 and 4.

(3) Diameter of Primary Particles

As pretreatment for observation of the boron nitride aggregated grains,the boron nitride particle prepared was embedded in an epoxy resin andthe mixture was processed by the CP (cross-section polisher) method. Thesample thus obtained was fixed on the test piece stage and subjected toosmium coating.

The cross section of the sample was observed under a scanning electronmicroscope (e.g., “JSM-6010LA” (manufactured by JEOL)) at an observationmagnification of 2000 to 5000 times. The crosssectional particle imageobtained was sent to an image analysis software, for example “Mac-view”,for determination of the long side length. The long side lengths of 100pieces of crosssectional particles arbitrarily chosen were determinedand the average thereof was used as the average long side length. Thestandard deviation of the long side length was also determined. FIG. 3shows an SEM image of Example 1.

(4) Thermal Conductivity

Thermal conductivity (H; W/(m·K)) was determined from thermaldiffusivity (A:m²/sec), specific density (B:kg/m³), and specific heatcapacity (C:J/(kg·K)) according to the formula: H=A×B×C.

The thermal diffusivity was determined by the laser flash method, as asheet of 10 mm×10 mm (width)×0.5 mm (thickness) was prepared as the testsample. The analyzer used was a xenon flash analyzer (“LFA447NanoFlash”manufactured by NETZSCH). The specific density was determined by theArchimedes method. The specific heat capacity was determined on a DSC(“ThermoPlus Evo DSC8230” manufactured by Rigaku Corporation)

A thermal conductivity of 10 W/mK or more was considered satisfactory inthe present invention.

(5) Residual Rate of BN Aggregated Grains

BN aggregated grains residual rate was determined for evaluation of theproperties in grain strength when the boron nitride powder obtained ismixed with a resin. A boron nitride powder was mixed, in an amount of 10vol %, with an epoxy resin (“Epikote 807” produced by MitsubishiChemical Corporation) and a hardener (“Akumex H-84B”, produced by NihonGosei Kako).

The mixture was processed in a three-roll mill “M-50” manufactured byNagase Screen Printing at a gap distance of 100 μm, applied then on aPET sheet to a thickness of 1.0 mm and defoamed at a reduced pressure of500 Pa for 10 minutes. The applied mixture was then subjected topress-heating pressurization under a condition of a temperature of 150°C. and a pressure of 160 kg/cm² for 60 minutes, to give a sheet having athickness of 0.5 mm.

The sheet was subjected to a crosssectional observation similar to thatused for determination of primary particle size above to determine thenumber of aggregate particles present in 20 visual field observed at amagnification of 200 to 1000 times. Sheets without processing in thethree-roll mill were also similarly analyzed for determination of thenumber of aggregated grains. Those having an aggregated grain residualrate of 80% or more was considered satisfactory and indicated by 0 inthe table and those having a residual rate of 80% or less wereconsidered unsatisfactory and indicated by x.

(6) Carbon Content

Carbon content was determined on a simultaneous carbon/sulfur analyzer“CS-444LS” (manufactured by LECO).

(7) Viscosity

In preparing the sample for viscosity measurement, boron nitride powderwas added to 100 parts of a naphthalene-type epoxy resin (HP4032produced by DIC) and 10 parts of a hardener imidazole (2E4 MZ-CN,produced by Shikoku Corporation) and the mixture was kneaded in aplanetary centrifugal mixer (ARV-310 manufactured by ThinkyCorporation). Samples were prepared at a boron nitride powder loadingrate of 25 vol % and the viscosities of the samples were compared in alow-shear rate region. The viscosity was determined on a rheometerMCR300 manufactured by Anton-Paar at a shear rate of 0.11/sec and thevalue was used as the evaluation value. Filling property may beconsidered higher when the viscosity is lower and a viscosity of50·Pa·sec or less was considered satisfactory.

(8) X-Ray Photoelectron Spectroscopy Analysis:

The amount of metals present on the surface of boron nitride wasdetermined by analyzing treated powder on K-Alpha X-Ray photoelectronspectrometer manufactured by Thermo Fisher under the conditions of anexcitation source of Al—X-ray with monochrometer and a measurementregion of 400×200 μm. Semi-quantitative values of detected metalelements were estimated from the integral values of the detectedelements B, N, C, O, and respective metals. The values are normallyrepresented by atom number rate (atm %). The X-Ray photoelectronspectrometer had a detection depth of 10 nm from the surface.

(9) Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS):

Functional groups on the surface of boron nitride were analyzed on atime-of-flight secondary ion mass spectrometer PHI nanoTOF IImanufactured by ULVAC-PHI, Inc. When the results of mass spectrometryindicate detection of multiple fragment peaks derived from the couplingagent, ◯ is shown in the column of Surface functional group and x isshown there when the results show no detection of the fragment peaks.

EXAMPLES

Hereinafter, the present invention will be described more in detail withreference to Examples, Test Examples, and Comparative Examples. Itshould be understood that the present invention is not limited to theExamples described below.

Example 1

In Example 1, a boron nitride powder was prepared in the steps ofpreparing boron carbide, nitridating it under pressure and decarburizingand crystallizing the product, as described below.

(Preparation of Boron Carbide)

100 parts of orthoboric acid (hereinafter, boric acid) produced by NihonDenko and 35 parts of acetylene black (HS100) produced by Denka Co.,Ltd. were mixed in a Henschel Mixer and the mixture was placed in agraphite crucible and calcined in an arc furnace under an argonatmosphere at 2200° C. for 5 hours, to give a boron carbide (B₄C). Theboron carbide lumps prepared was pulverized in a ball mill for 1 hourand sieved with a sieve screen into particles having a particle diameterof 75 μm or less. The particles were washed with aqueous nitric acidsolution for removal of impurities such as iron, and filtered and dried,to give a boron carbide powder having an average particle diameter of 20μm. The boron carbide powder obtained had a carbon content of 20.0%.

(Pressure-Nitridating Step)

The boron carbide prepared was placed in a boron nitride crucible andincinerated in a resistance-heating furnace under a condition of anitrogen gas atmosphere at 2000° C. and a pressure of 9 atmosphericpressure (0.8 MPa) for 10 hours, to give a boron carbide nitride(B₄CN₄).

(Decarburization Crystallization Step)

100 parts of the boron carbide nitride prepared and 200 parts of boricacid were mixed in a Henschel Mixer. The mixture was placed in a boronnitride crucible and heated from room temperature to 1000° C. at aheating rate of 10° C./min and from 1000° C. upward at a heating rate of2° C./min in a resistance-heating furnace under a nitrogen gasatmosphere and heated at a retention temperature of 2000° C. for aretention period of 10 hours under the condition of a pressure of 0.3MPa, to give bulky boron nitride aggregated grains in which primaryparticles are aggregated.

The boron nitride aggregated grains prepared was pulverized in a mortarfor 10 minutes and classified with a sieve screen and with a nylon sievehaving a sieve opening of 75 μm.

Pulverization and classification of the incinerated product gave a boronnitride powder containing bulky boron nitride aggregated grains in whichprimary particles are aggregated (hereinafter, also referred to as“aggregated boron nitride powder”).

The boron nitride aggregated grains prepared had a carbon content of0.08%.

(Mixing with Resin)

For evaluation of the properties of the boron nitride powder obtained asa filler for resins, 100 parts of a naphthalene-type epoxy resin(HP4032, produced by DIC) and 10 parts of a hardener imidazole (2E4MZ-CN produced by Shikoku Corporation) were mixed with the boron nitridepowder content of 50 vol % and the mixture was applied on a PET sheet toa thickness of 1.0 mm and defoamed at a reduced pressure of 500 Pa for10 minutes. The coated sheet was then heated and pressurized under thecondition at a temperature of 150° C. and a pressure of 160 kg/cm² for60 minutes, to give a sheet of 0.5 mm.

The case when the slurry after mixing was less flowable and cannot becasted was indicated in the table by “unfavorable filling property”.

Example 2

In Example 2, an aggregated boron nitride powder was prepared under acondition similar to that in Example 1, except that “a boron carbidehaving an average particle diameter of 8 μm (carbon content: 20.1%)” wasprepared, as the pulverization period was elongated to 2 hours and asieve screen having an opening of 45 μm was used when boron carbide wasprepared.

Example 3

In Example 3, an aggregated boron nitride powder was prepared under acondition similar to that in Example 1, except that: a “boron carbidehaving an average particle diameter of 40 μm (carbon content: 19.2%)”was prepared, as pulverization was carried out for 0.5 hour duringpreparation of boron carbide and a sieve screen having an opening of 150μm was used; and the sieve used after the decarburizationcrystallization step was changed to that having an opening of 150 μm.

Example 4

In Example 4, an aggregated boron nitride powder was prepared under acondition similar to that in Example 1, except that the heating rate inthe decarburization crystallization step was changed to 5° C./min.

Example 5

In Example 5, an aggregated boron nitride powder was prepared under acondition similar to that in Example 1, except that the retention periodin the decarburization crystallization step was changed to 20 hours.

Example 6

In Example 6, an aggregated boron nitride powder was prepared under acondition similar to that in Example 1, except that the retentiontemperature in the decarburization crystallization step was changed to1800° C.

Example 7

In Example 7, an aggregated boron nitride powder was prepared under acondition similar to that in Example 1, except that the heating ratefrom 1000° C. in the decarburization crystallization step was changed to0.5° C./min.

Comparative Example 1

In Comparative Example 1, an aggregated boron nitride powder wasprepared under a condition similar to that in Example 1, except that theheating rate from 1000° C. in the decarburization crystallization stepwas changed to 10° C./min.

Comparative Example 2

In Comparative Example 2, an aggregated boron nitride powder wasprepared under a condition similar to that in Example 1, except that aboron carbide having an average particle diameter of 5 μm (carboncontent: 20.3%)” was prepared, as the pulverization period during boroncarbide preparation was changed to 10 hours and a sieve screen having anopening of 45 μm was used.

Comparative Example 3

In Comparative Example 3, an aggregated boron nitride powder wasprepared under a condition similar to that in Example 1, except that: aboron carbide having an average particle diameter of 60 μm (carboncontent: 20.4%) was prepared, as the pulverization period during theboron carbide preparation was changed to 0.2 hour and a sieve screenhaving an opening of 250 μm was used; and a sieve having an opening of250 μm was used after the decarburization crystallization step.

Comparative Example 4

In Comparative Example 4, an aggregated boron nitride powder wasprepared under a condition similar to that in Example 1, except that theretention period in the decarburization crystallization step was changedto 40 hours.

Comparative Example 5

In Comparative Example 5, an aggregated boron nitride powder wasprepared under a condition similar to that in Example 1, except that theretention temperature in the decarburization crystallization step waschanged to 1700° C.

Comparative Example 6

In Comparative Example 6, an aggregated boron nitride powder wasprepared under a condition similar to that in Example 1, except that aboron carbide having a carbon content of 21.7% (average particlediameter: 20 μm) was prepared, as 45 parts of acetylene black was usedin preparation of the boron carbide.

Comparative Examples 7 and 8

Two kinds of commercially available boron nitride powders (commercialproducts A and B) were evaluated similarly to Examples 1 to 7 andComparative Examples 1 to 6. Results obtained from the commercialproduct A are summarized as results of Comparative Example 7 and thoseobtained from the commercial product B as the results of ComparativeExample 8.

The results shown in Tables 1 and 2 indicate the followings:

<Average Particle Diameter>

As shown in Examples 1 to 7 (see for example Examples 2 and 3), boronnitride powders having an average particle diameter of 22 to 80 gave afavorable thermal conductivity and a favorable residual rate of BNaggregated grains. In contrast as shown in Comparative Example 2, theboron nitride powder is not favorable when it has an average particlediameter of 10 μm or less and, as shown in Comparative Example 3, theboron nitride powder was also unfavorable when it has an averageparticle diameter of 110 μm or more.

<Grain Strength (at 63.2%)>

As shown in Examples 1 to 7 (e.g., see Example 4), a grain strength (at63.2%) of 8.0 MPa or more leads to favorable thermal conductivity and BNaggregated grain residual rate. In contrast as shown in ComparativeExamples 1, 4, 6 to 8, a grain strength (at 63.2%) of 6 MPa or less gaveunfavorable results.

<Grain Strength (at 20.0%)>

As shown in Examples 1 to 7 (see in particular Example 4), a grainstrength (at 20.0%) of 4.6 MPa or more gave favorable thermalconductivity and BN aggregated grain residual rate. In contrast as shownin Comparative Examples 1, 4, and 6 to 8, a grain strength (at 20.0%) of3.5 MPa or less gave unfavorable results.

<Long Side Length of Primary Particles>

As shown in Examples 1 to 7 (see for example Examples 6 and 5), anaverage long side length of the primary particles of 1.7 to 3.2 μm gavefavorable thermal conductivity and BN aggregated grain residual rate. Incontrast as shown in Comparative Example 5, an average long side lengthof the primary particles of 1.3 μm or less gave unfavorable results and,as shown in Comparative Example 4, an average long side length of theprimary particles of 4.0 μm or more also gave unfavorable results.

<Standard Deviation>

As shown in Examples 1 to 7 (see in particular Examples 4 and 5), astandard deviation of 1.0 μm or less gave favorable thermal conductivityand BN aggregated grain residual rate. In contrast as shown inComparative Examples 1 and 4, a standard deviation of 1.3 μm or moregave unfavorable results.

TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6Example 7 BN powder BN powder Average particle 45 22 80 45 45 45 45diameter μm BN aggregated Grain strength 11 12 10 8.0 9.0 11 20 grainsMPa (63.2%) BN aggregated Grain strength 7.0 7.5 6.5 4.6 5.0 7.0 13grains MPa (20.0%) Primary Long side 2.5 2.1 2.5 2.5 3.2 1.7 2.5particles length Primary Standard 0.7 0.6 0.7 1.0 1.0 0.7 0.4 particlesdeviation Thermal conductivity W/mK 12 11 11 11 10 10 13 BN aggregatedgrain residual rate ∘ ∘ ∘ ∘ ∘ ∘ ∘

TABLE 2 Comparative Comparative Comparative Comparative Example 1Example 2 Example 3 Example 4 BN powder BN powder Average particle 45 10110 45 diameter μm BN aggregated Grain strength 6 11 11 5.5 grains MPa(63.2%) BN aggregated Grain strength 3.5 7.0 7.0 3.0 grains MPa (20.0%)Primary Long side 2.7 2.5 2.5 4.0 particles length Primary Standard 1.30.7 0.7 1.3 particles deviation Thermal conductivity W/mK 8 7 Notavailable 8 BN aggregated grain residual rate x ∘ x x ComparativeComparative Comparative Comparative Example 5 Example 6 Example 7Example 8 BN powder BN powder Average particle 45 45 36 75 diameter μmBN aggregated Grain strength 11 7.5 7.8 3.5 grains MPa (63.2%) BNaggregated Grain strength 7.0 3.5 3.0 1.6 grains MPa (20.0%) PrimaryLong side 1.3 2.2 4.9 5.5 particles length Primary Standard 0.5 0.6 1.62.3 particles deviation Thermal conductivity W/mK 8 8 8 7 BN aggregatedgrain residual rate ∘ x x x Note: Comparative Example 2: boron carbidehaving an average particle diameter of 5 μm; Comparative Example 3:boron carbide having an average particle diameter of 60 μm; ComparativeExample 6: boron carbide having a carbon content of 21.7%

Hereinafter, other embodiments of the present invention will bedescribed in detail with reference to Examples, Test Examples, andComparative Examples, and it should be understood that the invention isnot restricted thereby.

Example 8 (Preparation of Boron Carbide)

100 parts of orthoboric acid (hereinafter boric acid) produced by NihonDenko and 35 parts of acetylene black (HS100) produced by Denka Co.,Ltd. were mixed in a Henschel Mixer and the mixture was placed in agraphite crucible and calcined in an arc furnace under an argonatmosphere at 2200° C. for 5 hours, to give a boron carbide (B₄C). Theboron carbide lumps prepared were pulverized in a ball mill for 1 hourand sieved with a sieve screen into particles having a particle diameterof 75 μm or less. The particles were washed with aqueous nitric acidsolution for removal of impurities such as iron, and filtered and dried,to give a boron carbide powder having an average particle diameter of 20μm (carbon content: 20%).

(Pressure-Nitridating Step)

The boron carbide prepared was placed in a boron nitride crucible andincinerated in a resistance-heating furnace under a condition of anitrogen gas atmosphere at 2000° C. and a pressure of 9 atmosphericpressure (0.8 MPa) for 10 hours, to give a boron carbide nitride(B₄CN₄).

(Decarburization Crystallization Step)

100 parts of the boron carbide nitride prepared and 200 parts of boricacid were mixed in a Henschel Mixer. The mixture was placed in a boronnitride crucible and heated from room temperature to 1000° C. at aheating rate of 10° C./min and from 1000° C. upward at a heating rate of0.5° C./min in a resistance-heating furnace under a nitrogen gasatmosphere and additionally heated at a retention temperature of 2000°C. for a retention period of 10 hours under the condition of a pressureof 0.3 MPa, to give bulky boron nitride aggregated grains in whichprimary particles are aggregated.

The boron nitride aggregated grains prepared was pulverized in a mortarfor 10 minutes and classified with a sieve screen and with a nylon sievehaving a sieve opening of 75 μm.

Pulverization and classification of the incinerated product gave a boronnitride powder containing bulky boron nitride aggregated grains in whichprimary particles are aggregated (grain strength (at 20.0%): 13 MPa,average particle diameter: 45 μm, average long side length of theprimary particles: 2.5 μm, standard deviation: 0.4 μm).

(Surface Treatment Condition)

The boron nitride powder prepared was subjected to surface modificationtreatment in a Henschel Mixer, under the condition of 1400 parts ofaqueous hydrogen peroxide (water:hydrogen peroxide=1:0.05 (wt % withrespect to 100 parts of boron nitride for 20 minutes. The treated slurrywas sieved through a 75 μm sieve for removal only of the medium and thesieved slurry was filtered and washed. 1000 parts of isopropyl alcoholand 4 parts of a coupling agent KR-TTS (isopropyl triisostearoyltitanate) produced by Ajinomoto Fine-Techno Co., Ltd. were added to thewet cake after filtration with respect to 100 parts of boron nitride andthe mixture was allowed to react at 70° C. for 3 hours for couplingtreatment. The treated powder was filtered and washed and then dried at80° C., to give a surface-treated aggregated boron nitride powder ofExample 8.

Crosssectional observation of the surface-treated boron nitrideaggregated grains under electron microscope showed that the powdercontains aggregated hexagonal h-BN primary particles having an averagelong side length of the scaly hexagonal boron nitride primary particlesat 2.5 μm and a standard deviation thereof at 0.4 μm.

(Mixing with Resin)

The surface-treated aggregated boron nitride powder obtained was mixedwith 100 parts of a naphthalene-type epoxy resin (HP4032 produced byDIC) and 10 parts of a hardener imidazole (2E4MZ-CN produced by ShikokuChemical Corporation) at a rate of 50 vol % and the mixture was appliedon a PET sheet to a thickness of 1.0 mm and defoamed under a reducedpressure of 500 Pa for 10 minutes. The mixture was then heat-treatedunder pressure under a condition of a temperature of 150° C. and apressure of 160 kg/cm² for 60 minutes, to give a 0.5-mm sheet.

Example 91

In Example 9, a surface-treated aggregated boron nitride powder ofExample 9 was prepared under a condition similar to that in Example 8,except that a boron nitride powder containing boron nitride aggregatedgrains having a grain strength of 10 MPa was used as the raw materialand the second-step heating rate in the decarburization crystallizationstep was changed to 2° C./min.

The raw material aggregated boron nitride powder had a grain strength(at 20.0%) of 7 MPa, an average particle diameter of 45 μm, an averagelong side length of the primary particles of 2.5 μm, and a standarddeviation of 0.7 μm.

Crosssectional observation of the surface-treated boron nitrideaggregated grains under electron microscope showed that the powdercontains aggregated hexagonal h-BN primary particles, having an averagelong side length of the scaly hexagonal boron nitride primary particlesat 2.5 μm and a standard deviation thereof at 0.7 μm.

Example 10

In Example 10, a boron nitride powder containing boron nitrideaggregated grains having an average particle diameter of 80 μm ofExample 10 was prepared under a condition similar to the steps frompreparation of boron carbide to decarburization and crystallization ofExample 8, except that: a boron carbide having an average particlediameter of 40 μm was prepared, as the pulverization for preparation ofboron carbide in preparation of the boron carbide of Example 8 wasperformed for 0.5 hour and a sieve screen having an opening of 150 μmwas used; and a sieve screen having an opening of 150 μm was used in thedecarburization crystallization step.

The raw material aggregated boron nitride powder obtained had a grainstrength (at 63.2%) of 20 MPa, a grain strength (at 20.0%) of 6.0 MPa,an average particle diameter of 80 μm, an average long side length ofthe primary particles at 2.5 μm, and a standard deviation thereof at0.7.

In addition, a surface-treated aggregated boron nitride powder ofExample 10 was prepared under a condition similar to the surfacetreatment condition in Example 8, except that the boron nitride powdercontaining boron nitride aggregated grains having an average particlediameter of 80 μm of Example 10 was used under the surface treatmentcondition of Example 8.

Example 11

In Example 11, a boron nitride powder containing boron nitrideaggregated grains having an average particle diameter of 22 μm ofExample 11 was prepared under a condition similar to the steps frompreparation of boron carbide to decarburization and crystallization ofExample 8, except that a boron carbide having an average particlediameter of 8 μm was prepared, as the pulverization period duringpreparation of the boron carbide was changed to 2 hours and the sievescreen used was changed to a sieve screen having an opening of 45 μm inpreparation of the boron carbide of Example 8.

The raw material aggregated boron nitride powder had a grain strength(at 63.2%) of 20 MPa, a grain strength (at 20.0%) of 6.0 MPa, an averageparticle diameter of 22 μm, an average long side length of the primaryparticles at 2.0 μm and a standard deviation thereof at 0.7.

In addition, a surface-treated aggregated boron nitride powder ofExample 11 was prepared under a condition similar to that of Example 8,except that a boron nitride powder containing boron nitride aggregatedgrains having an average particle diameter of 22 μm of Example 11 wasused under the surface treatment condition of Example 8.

Example 12

In Example 12, a surface-treated aggregated boron nitride powder ofExample 12 was prepared under a condition similar to that of Example 8,except that the amount of the coupling agent was changed to 30 parts.

Example 13

In Example 13, a surface-treated aggregated boron nitride powder ofExample 13 was prepared under a condition similar to that of Example 8,except that the amount of the coupling agent was changed to 1 part.

Example 14

In Example 14, a surface-treated aggregated boron nitride powder ofExample 14 was prepared under a condition similar to that of Example 8,except that the coupling agent used was changed to KR-46B(tetraoctyl-bis(ditridecyl phosphite) titanate) produced by AjinomotoFine-Techno Co., Ltd.

Example 15

In Example 15, a surface-treated aggregated boron nitride powder ofExample 15 was prepared under a condition similar to that of Example 8,except that the coupling agent used was changed to X12-982S (polymericepoxysilane-based) produced by Shin-Etsu Silicones.

Example 16

In Example 16, a surface-treated aggregated boron nitride powder ofExample 16 was prepared under a condition similar to that of Example 8,except that the coupling agent used was changed to3-glycidyloxypropyltrimethoxysilane produced by Tokyo Chemical IndustryCo., Ltd.

Example 17

In Example 17, a surface-treated aggregated boron nitride powder ofExample 17 was prepared under a condition similar to that of Example 8,except that the coupling agent used was changed totetrakis(2,4-pentanedionato)zirconium (IV) [another name in Japanese:zirconium (IV) acetylacetonate)] produced by Tokyo Chemical IndustryCo., Ltd.

Example 181

In Example 18, a surface-treated aggregated boron nitride powder ofExample 18 was prepared under a condition similar to that of Example 8,except that the coupling agent used was changed to Orgatics AL-3200[aluminum bisethylacetoacetate monoacetylacetonate ((C₅H₇O₂) (C₆H₉O₃)₂)]produced by Matsumoto Fine Chemical Co., Ltd.

Example 191

A surface-treated aggregated boron nitride powder of Example 19 wasprepared under a condition similar to that of Example 8, except that thecoupling agent used under the surface treatment condition was changed toKBM-140 [p-styryltrimethoxysilane] produced by Shin-Etsu Silicones.

Example 201

A surface-treated aggregated boron nitride powder of Example 20 wasprepared under a condition similar to that of Example 8, except that thecoupling agent used under the surface treatment condition was changed toKBE-9007 [3-isocyanatopropyltriethoxysilane] produced by Shin-EtsuSilicones.

Example 21

A surface-treated aggregated boron nitride powder of Example 21 wasprepared under a condition similar to that of Example 8, except that thecoupling agent used under the surface treatment condition was changed toZ-6300 [vinyltrimethoxysilane] produced by Dow Corning Toray.

Example 22

A surface-treated aggregated boron nitride powder of Example 22 wasprepared under a condition similar to that of Example 8, except that thecoupling agent used under the surface treatment condition was changed toZ-6187 [cyclohexylmethyldimethoxysilane] produced by Dow Corning Toray.

Example 23

In Example 23, a surface-treated aggregated boron nitride powder ofExample 23 was prepared under a condition similar to that of Example 8,except that 1400 parts of aqueous hydrogen peroxide (water:hydrogenperoxide=1:0.05 (wt % ratio)) with respect to 100 parts of the boronnitride was changed to 1400 parts of aqueous nitrous acid (water:nitrousacid=1:0.05 (wt % ratio)) with respect to 100 parts of boron nitride.

Example 24

In Example 24, a surface-treated aggregated boron nitride powder ofExample 24 was prepared under a condition similar to that of Example 8,except that 1400 parts of aqueous hydrogen peroxide (water:hydrogenperoxide=1:0.05 (wt % ratio)) with respect to 100 parts of boron nitridewas changed to 1400 parts of aqueous permanganate salt(water:permanganic acid salt=1:0.03 (wt % ratio)) with respect to 100parts of boron nitride.

Test Example 1

In Test Example 1, a boron nitride powder containing boron nitrideaggregated grains was prepared under a condition similar to that inExample 8 (in the steps from preparation of boron carbide todecarburization and crystallization), except that no surfacemodification treatment and no coupling treatment were performed.

Test Example 2

In Test Example 2, an aggregated boron nitride powder was prepared undera condition similar to that in Example 8, except that the couplingtreatment was performed without the surface modification treatment in aHenschel Mixer during surface treatment.

Test Example 3

In Test Example 3, an aggregated boron nitride powder was prepared undera condition similar to that in Example 8, except that the secondcalcining rate during the decarburization crystallization was changed to5° C./min and a boron nitride powder containing boron nitride aggregatedgrains having a grain strength of 8 MPa was used.

Test Example 4

In Test Example 4, an aggregated boron nitride powder was prepared undera condition similar to that in Example 14, except that the couplingtreatment was performed without the Henschel Mixer treatment for surfacemodification during the surface treatment.

Test Example 5

In Test Example 5, an aggregated boron nitride powder was prepared undera condition similar to that in Example 15, except that the couplingtreatment was performed without the Henschel Mixer treatment for surfacemodification during the surface treatment.

Test Example 6

In Test Example 6, an aggregated boron nitride powder was prepared undera condition similar to that in Example 17, except that the couplingtreatment was performed without the Henschel Mixer treatment for surfacemodification during the surface treatment.

Test Example 7

In Test Example 7, an aggregated boron nitride powder was prepared undera condition similar to that in Example 18, except that the couplingtreatment was performed without the Henschel Mixer treatment for surfacemodification during the surface treatment.

Test Example 8

In Test Example 8, an aggregated boron nitride powder was prepared undera condition similar to that in Example 18, except that the HenschelMixer treatment was not performed for surface modification during thesurface treatment and the coupling agent used was changed to Ken-React(trade name) KZ TPP (trade name) Zirconate produced by Kenrich,zirconium (IV) 2,2-bis(2-propenolatomethyl)butanolato,cyclo-di[2,2-(bis-2-propenolatomethyl)butanolato] pyrophosphato-O,O.

Test Example 9

In Test Example 9, an aggregated boron nitride powder was prepared undera condition similar to that in Example 8, except that a boron carbidehaving an average particle diameter of 5 μm was prepared, as thepulverization period of boron carbide preparation was elongated to 10hours and a sieve screen having an opening of 45 μm was used. Inaddition, an aggregated boron nitride powder was prepared under acondition similar to that in Example 8, except that a boron nitridepowder containing boron nitride aggregated grains having an averageparticle diameter of 10 μm was used under the surface treatmentcondition.

Results of Examples 8 to 25 and Examples 1 to 9 are summarized in Tables3 and 4. The value of grain strength (at a cumulative breakdown rate of63.2%) is shown as the grain strength (crushing strength) in Tables 3and 4.

The raw material aggregated boron nitride powders used in Examples 8 and9 are respectively equivalent to the boron nitride powders in Example 7and Example 1 containing boron nitride aggregated grains that are formedby aggregation of primary particles.

The results shown in Tables 3 and 4 indicate the followings:

<Surface Treatment>

The aggregated boron nitride powders of Examples 8 to 24, which at leastgave a viscosity of 40 Pa·s or less, were superior in filling propertyinto resin. The aggregated boron nitride powders of Examples 8 to 24,which at least gave a viscosity of half or less, as compared with theaggregated boron nitride powder of Test Example 1 that was notsurface-treated, could improve the filling property into resin of theaggregated boron nitride powder of Test Example 1.

As shown in Examples 8 to 24, the boron nitride aggregated grains showedfavorable filling property into resin, even when the boron nitrideaggregated grains had various organic functional groups provided on thesurface by surface treatment.

As shown in Examples 8 to 24 (see for example Examples 1, 23, and 24),use of an oxidizer such as hydrogen peroxide, nitric acid, orpermanganic acid in surface treatment leads to improvement in fillingproperty into resin.

<Atm %>

the boron nitride aggregated grains in Examples 8 to 24 (see for exampleExamples 12 and 3), which had at least Si, Ti, Zr, Ce, Al, Mg, Ge, Ga,and V in an amount of 0.1 atm % or more and 3.0 atm % or less in itscomposition on the surface of 10 nm, were superior in filling propertyinto resin. In contrast, the boron nitride aggregated grains, forexample in Test Examples 1, 2, and 4 to 8, which had the metal elementsin an amount of detection limit or less in its composition on thesurface of 10 nm, had an unfavorable viscosity of 85 Pa·s or more.

<Crushing Strength (Grain Strength (at 63.2%)>

As shown in Examples 8 to 24 (see for example Example 9), when the boronnitride aggregated grains after surface treatment had a grain strength(at 63.2%) of 5.0 MPa or more, the aggregated grains were superior infilling property into resin. In contrast as shown in Example 3, when thesurface-treated boron nitride aggregated grains had a grain strength (at63.2%) of 3 MPa, the aggregated grains were unfavorable, as they gave aviscosity of 60 Pa·s.

As shown in Examples 8 to 24, when the aggregated grains beforetreatment had a grain strength (at 63.2%) of 10 MPa or more, they gave aviscosity of half or less of the viscosity of Test Example 1. As shownin Test Example 3, when the aggregated grains before treatment had agrain strength (at 63.2%) of 8 MPa, the aggregated grains after surfacetreatment gave a viscosity of 60 Pa·s, which was 40% lower than theviscosity of Test Example 1. The result indicates that it is desirableto use boron nitride aggregated grains having a higher grain strength asthe raw material for further improvement in filling property into resinof the aggregated boron nitride powder.

<Average Particle Diameter>

As shown in Examples 8 to 24 (see for example Examples 10 and 11), boronnitride aggregated grains having an average particle diameter of 20 to80 μm after surface treatment were favorable in filling property intoresin. In contrast as shown in Example 9, those having an averageparticle diameter of 10 μm after surface treatment were unfavorable, asthey gave a viscosity of 60 Pa·s.

TABLE 3 Example Example Example Example Example Example Example ExampleExample 8 9 10 11 12 13 14 15 16 BN Raw Grain strength 20 10 20 20 20 2020 20 20 aggregated material before treatment grain (63.2%) MPa AfterGrain strength 10 5 10 10 10 10 10 10 10 surface after treatmenttreatment (63.2%) MPa Post-treatment 45 45 80 20 45 45 45 45 45 averageparticle diameter μm Post-treatment 0.5 0.5 0.5 0.5 0.1 3 0.5 0.5 0.5surface metal content atm % Metal element Ti Ti Ti Ti Ti Ti Ti Si SiPost-treatment ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ surface functional groups Viscosity Pa· S 20 30 20 40 25 20 20 20 20 Example Example Example Example ExampleExample Example Example 17 18 19 20 21 22 23 24 BN Raw Grain strength 2020 20 20 20 20 20 20 aggregated material before treatment grain (63.2%)MPa After Grain strength 10 10 10 10 10 10 10 10 surface after treatmenttreatment (63.2%) MPa Post-treatment 45 45 45 45 45 45 45 45 averageparticle diameter μm Post-treatment 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5surface metal content atm % Metal element Zr Al Si Si Si Si Ti TiPost-treatment ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ surface functional groups Viscosity Pa ·S 20 20 20 20 20 20 20 20

TABLE 4 Test Test Test Test Test Test Test Test Test Example ExampleExample Example Example Example Example Example Example 1 2 3 4 5 6 7 89 BN Raw Grain strength 20 20 8 20 20 20 20 20 20 aggregated materialbefore treatment grain (63.2%) MPa After Grain strength — 18 3 18 18 1818 18 10 treatment after treatment (63.2%) MPa Average particle 45 45 4545 45 45 45 45 10 diameter μm Surface metal detection detection 0.5detection detection detection detection detection 0.5 content atm %limit or limit or limit or limit or limit or limit or limit or less lessless less less less less Metal element Ti Ti Ti Ti Si Zr Al Zr TiSurface functional x x ∘ x x x x x ∘ groups Viscosity Pa · S 100  90 6090 90 85 85 85 60

INDUSTRIAL APPLICABILITY

Particularly preferably, the present invention relates to a boronnitride powder superior in thermal conductivity for use in resincompositions for the insulation layer of printed wiring boards and forthermal interface materials, a method for producing the same, and athermally conductive resin composition comprising the same.

The present invention is used favorably, specifically as a raw materialfor heat-dissipating parts used in heat-generating electronic parts suchas power devices.

The thermally conductive resin composition according to the presentinvention can be used widely, for example as a heat-dissipating part.The surface-treated aggregated boron nitride powder in anotherembodiment of the present invention can be used widely, for example as aheat-dissipating part.

The present technology includes the following aspects:

[1] A boron nitride powder comprising boron nitride aggregated grainsthat are formed by aggregation of hexagonal boron nitride that is scalyin primary particle: the powder having the following characteristics (A)to (C),(A) the primary particles of the scaly hexagonal boron nitride have anaverage long side length of 1.5 μm or more and 3.5 μm or less and astandard deviation of 1.2 μm or less;(B) the boron nitride aggregated grains have a grain strength of 8.0 MPaor more at a cumulative breakdown rate of 63.2% and a grain strength of4.5 MPa or more at a cumulative breakdown rate of 20.0%; and(C) the boron nitride powder has an average particle diameter of 20 μmor more and 100 μm or less.[2] The boron nitride powder of [1] above, wherein the boron nitridepowder of (C) above has an average particle diameter of 30 μm or moreand 80 μm or less.[3] A method for producing a boron nitride powder, comprising thefollowing steps (a) and (b) of:(a) pressure-nitridating and calcining a boron carbide having an averageparticle diameter of 6 μm or more and 55 μm or less and a carbon contentof 18% or more and 21% or less and(b) heat-treating the boron carbide by heating it to a temperatureallowing initiation of decarburization, heating it to a retentiontemperature at a temperature rising rate of 5° C./min or less, andheating it at a temperature of 1750° C. or higher for a period longerthan 0.5 hour and shorter than 40 hours in a decarburizationcrystallization step after the pressure nitridation and calcination.[4] The method for producing a boron nitride powder of [3] above,wherein the boron carbide is pressure-nitridated and calcined at atemperature of 1800° C. or higher and a pressure of 0.7 MPa or more and1.0 MPa or less in the step (a).[5] A thermally conductive resin composition, comprising the boronnitride powder described in [1] or [2] above.[6] The boron nitride powder described in [1] or [2] above, wherein theboron nitride powder is prepared by the method for producing a boronnitride powder, comprising the following steps (a) and (b):(a) pressure-nitridating and calcining a boron carbide having an averageparticle diameter of 6 μm or more and 55 μm or less and a carbon contentof 18% or more and 21% or less and(b) heat-treating the boron carbide by heating it to a temperatureallowing initiation of decarburization, heating it to a retentiontemperature at a temperature rising rate of 5° C./min or less, andheating it at a temperature of 1750° C. or higher for a period longerthan 0.5 hour and shorter than 40 hours in a decarburizationcrystallization step after the pressure nitridation and calcination.[7] The boron nitride powder described in [1], [2], or [6] above,wherein the boron carbide is pressure-nitridated and calcined at atemperature of 1800° C. or higher and a pressure of 0.7 MPa or more and1.0 MPa or less in the step (a).[8] A surface-treated aggregated boron nitride powder, that is preparedby using the boron nitride powder of [1], [2], [6], or [7] above as theraw material, adding an oxidizer to the aggregated boron particles,wet-pulverizing or wet-crushing the particles for surface modificationtreatment of the particles and allowing reaction of the particles with ametal coupling agent, the surface-treated aggregated boron nitridepowder having the following characteristics (A) to (D):(A) the surface-treated boron nitride aggregated grains are formed byaggregation of hexagonal h-BN primary particles;(B) the surface-treated boron nitride aggregated grains have any one ormore of Si, Ti, Zr, Ce, Al, Mg, Ge, Ga and V in an amount of 0.1 atm %or more and 3.0 atm % or less in its composition on the surface of 10nm;(C) the surface-treated boron nitride aggregated grains have a crushingstrength of 5 MPa or more; and(D) the surface-treated aggregated boron nitride powder has an averageparticle diameter of 20 μm or more and 100 μm or less.[9] The surface-treated aggregated boron nitride powder described in [8]above, wherein an oxidizer and a water-soluble solvent were added duringthe surface modification treatment.[10] The surface-treated aggregated boron nitride powder described in[8] or [9] above, wherein the metal coupling agent is one or moreselected from titanium coupling agents, silane coupling agents,zirconium coupling agents, and aluminum coupling agents.[11] An aggregated boron nitride powder having the followingcharacteristics (A) to (D):(A) the boron nitride aggregated grains are formed by aggregation ofhexagonal h-BN primary particles;(B) the boron nitride aggregated grains have any one or more of Si, Ti,Zr, Ce, Al, Mg, Ge, Ga, and V in an amount of 0.1 atm % or more and 3.0atm % or less in its composition on the surface of 10 nm;(C) the boron nitride aggregated grains have a crushing strength of 5MPa or more; and(D) the aggregated boron nitride powder has an average particle diameterof 20 μm or more and 100 μm or less.[12] The aggregated boron nitride powder described in [11] above, havingthe following characteristic:(E) the boron nitride aggregated grains have organic functional groupson the surface.[13] The aggregated boron nitride powder described in [11] or [12]above, wherein the organic functional group present on the surface ofthe boron nitride aggregated grains is one or more selected from epoxygroups that may be substituted, styryl groups that may be substituted,alkyl groups that may be substituted, vinyl groups that may besubstituted, acetylacetate groups that may be substituted, acyl groupsthat may be substituted, isocyanate groups that may be substituted,cyclohexyl groups that may be substituted, and tetraoctyl bis(ditridecylphosphite) groups that may be substituted.[14] A method for producing a surface-treated aggregated boron nitridepowder comprising adding an oxidizer to a raw material bulky boronparticles having an average particle diameter of 20 μm or more and 100μm or less, a crushing strength of 10 MPa or more, wet-pulverizing orwet-crushing the mixture for surface modification treatment of theparticles, and allowing a reaction thereof with a metal coupling agent.[15] The method for producing a surface-treated aggregated boron nitridepowder described in [14] above, wherein an oxidizer and a water-solublesolvent are added during the surface modification treatment.[16] The method for producing a surface-treated aggregated boron nitridepowder described in [14] or [15] above, wherein the metal coupling agentis one or more selected from titanium coupling agents, silane couplingagents, zirconium coupling agents, and aluminum coupling agents.[17] A method for producing a surface-modified aggregated boron nitridepowder, comprising adding an oxidizer to a raw material aggregated boronnitride powder having an average particle diameter of 20 μm or more and100 μm or less and a crushing strength of 10 MPa or more andwet-pulverizing or wet-crushing the mixture for surface modificationtreatment of the particles.[18] A surface-modified aggregated boron nitride powder, prepared by themethod for producing a surface-modified aggregated boron nitride powderdescribed in [17] above.[19] A thermally conductive resin composition, comprising the aggregatedboron nitride powder described in any one of [11] to [13] above.

1. A surface-treated aggregated boron nitride powder, prepared by usingthe boron nitride powder as the raw material, adding an oxidizer to theboron nitride aggregated grains, wet-pulverizing or wet-crushing thegrains for surface modification treatment of the particles and allowingreaction of the particles with a metal coupling agent, wherein the boronnitride powder comprises boron nitride aggregated grains that are formedby aggregation of scaly hexagonal boron nitride primary particles, andhas the following characteristics (a) to (c): (a) the primary particlesof the scaly hexagonal boron nitride have an average long side length of1.5 μm or more and 3.5 μm or less and a standard deviation of 1.2 μm orless; (b) the boron nitride aggregated grains have a grain strength of8.0 MPa or more at a cumulative breakdown rate of 63.2% and a grainstrength of 4.5 MPa or more at a cumulative breakdown rate of 20.0%; and(c) the boron nitride powder has an average particle diameter of 20 μmor more and 100 μm or less, and wherein the surface-treated aggregatedboron nitride powder has the following characteristics (A) to (D): (A)the surface-treated boron nitride aggregated grains are formed byaggregation of hexagonal h-BN primary particles; (B) the surface-treatedboron nitride aggregated grains have any one or more of Si, Ti, Zr, Ce,Al, Mg, Ge, Ga, and V in an amount of 0.1 atm % or more and 3.0 atm % orless in its composition on the surface of 10 nm; (C) the surface-treatedboron nitride aggregated grains have a crushing strength of 5 MPa ormore; and (D) the surface-treated aggregated boron nitride powder has anaverage particle diameter of 20 μm or more and 100 μm or less.
 2. Thesurface-treated aggregated boron nitride powder according to claim 1,prepared as the oxidizer and a water-soluble solvent are added duringthe surface modification treatment.
 3. The surface-treated aggregatedboron nitride powder according to claim 1, wherein the metal couplingagent is one or more coupling agents selected from titanium couplingagents, silane coupling agents, zirconium coupling agents, and aluminumcoupling agents.
 4. An aggregated boron nitride powder, characterized byhaving the following characteristics (A) to (D): (A) the boron nitrideaggregated grains are formed by aggregation of hexagonal h-BN primaryparticles; (B) the boron nitride aggregated grains have any one or moreof Si, Ti, Zr, Ce, Al, Mg, Ge, Ga, and V in an amount of 0.1 atm % ormore and 3.0 atm % or less in its composition on the surface of 10 nm;(C) the boron nitride aggregated grains have a crushing strength of 5MPa or more; and (D) the aggregated boron nitride powder has an averageparticle diameter of 20 μm or more and 100 μm or less.
 5. The aggregatedboron nitride powder according to claim 4, characterized additionally byhaving a characteristic: (E) the boron nitride aggregated grains haveorganic functional groups on the surface.
 6. The aggregated boronnitride powder according to claim 5, wherein the organic functionalgroup present on the surface of the boron nitride aggregated grains isone or more groups selected from epoxy groups that may be substituted,styryl groups that may be substituted, alkyl groups that may besubstituted, vinyl groups that may be substituted, acetylacetate groupsthat may be substituted, acyl groups that may be substituted, isocyanategroups that may be substituted, cyclohexyl groups that may besubstituted and tetraoctyl bis(ditridecyl phosphite) groups that may besubstituted.
 7. A thermally conductive resin composition, comprising theaggregated boron nitride powder according to claim
 1. 8. A thermallyconductive resin composition, comprising the aggregated boron nitridepowder according to claim 4.